4-Hetaroylpyrazol derivatives and the use thereof as herbicides

ABSTRACT

Hetaroyl derivatives of the formula I                    
     where: 
     R 1  and R 2  are each hydrogen, nitro, halogen, cyano, thiocyanato, hydroxyl, mercapto, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -alkylsulfonyl or C 1 -C 6 -alkoxysulfonyl, where the last 6 radicals may be substituted and/or functionalized; phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl, where the last 5 radicals may be substituted; 
     Z is an unsubstituted or substituted four-membered unsaturated, partially or fully saturated chain consisting of three carbons and one nitrogen; 
     Q is unsubstituted or substituted hydroxypyrazole linked at position 4; 
     and their agriculturally useful salts. 
     A process for preparing the hetaroyl derivatives, compositions comprising them, and the use of these derivatives or these compositions comprising them for controlling undesirable plants.

HETAROYL DERIVATIVES

The present invention relates to novel hetaroyl derivatives of the formula I

where

¹ and R² are each hydrogen, nitro, halogen, cyano, thiocyanato, hydroxyl, mercapto, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂₋C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy, Cl-C₆-haloalkoxy, C₂-C₆-alkenyloxy, C₂-C₆-alkynyloxy, Cl-C₆-alkylthio, C₁-C6-haloalkylthio, C₂₋C₆-alkenylthio, C₂-C₆-alkynylthio, C₁-C₆-alkylsulfinyl, C₁-C₆-haloalkylsulfinyl, C₂-C₆alkenylsulfinyl, C₂-C₆alkynylsulfinyl, C₁-C₆alkylsulfonyl, C₁₋C₆haloalkylsulfonyl, C₂-C₆-alkenylsulfonyl, C₂-C₆-alkynylsulfonyl, C₁-C₆-alkoxysulfonyl, C₁-C₆-haloalkoxysulfonyl, C₂-C₆-alkenyloxysulfonyl, C₂-C₆-alkynyloxysulfonyl, phenyl, phenyloxy, phenylthio, phenylsulfinyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following groups: nitro, cyano, hydroxyl, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy;

Z is a building block from the group consisting of Z¹ to Z¹²

where

R³, R⁵, R⁷ and R⁹ are each nitro, cyano, hydroxyl, mercapto, C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₂-C₄-alkenyloxy, C₂-C₄-alkynyloxy, C₂-C₄-alkenylthio, C₂₋C₄-alkynylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-haloalkylsulfinyl, C₂-C₄-alkenylsulfinyl, C₂-C₄-alkynylsulfinyl, C₁-C₄-alkylsulfonyl, C₁-C₄-haloalkylsulfonyl, C₂-C₄-alkenylsulfonyl, C₂-C₄-alkynylsulfonyl, C₁-C₄-alkoxysulfonyl, C₁-C₄-haloalkoxysulfonyl, C₂-C₄-alkenyloxysulfonyl, C₂₋C₄-alkynyloxysulfonyl, —NR¹²R¹³, —CO₂R¹², —CONR¹²R¹³, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following groups: nitro, cyano, hydroxyl, Cl-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy; or one of the radicals mentioned under R⁴;

R⁴, R⁶′ R⁸ and R¹⁰ are each hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio or C₁-C₄-haloalkylthio;

or

a —CR³R⁴—, —CR⁵R⁶—, —CR⁷R⁸— or —CR⁹R¹⁰— unit may be replaced by C=O or C=NR¹³;

R¹¹ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₆-alkylcarbonyl, C₁-C₆-haloalkylcarbonyl, —CO₂R¹², —CONR¹²R¹³ or SO₂R¹²;

R¹² is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl or phenyl, where the last radical may be partially or fully halogenated and may carry one to three of the following radicals: nitro, cyano, hydroxyl, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy;

R¹³ is C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy or one of the radicals mentioned under R¹²;

Q is a hydroxypyrazole, linked through position 4, of the formula II

where

R¹⁴ is C₁-C₆-alkyl, C₁-C₆-haloalkyl or phenyl, where the last radical may be partially or fully halogenated and may carry one to three of the following radicals: nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy;

R¹⁵ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkylcarbonyl, C₁-C₆-haloalkylcarbonyl, C₁-C₆-alkoxycarbonyl, C₁-C₆-alkylsulfonyl, C₁-C₆-haloalkylsulfonyl, phenyl-C₁-C₄-alkyl, phenylcarbonyl-C₁-C4-alkyl, phenylcarbonyl, phenoxycarbonyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following radicals: nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy;

R¹⁶ is hydrogen, C₁-C₆-alkyl or C₁-C₆-haloalkyl;

and their agriculturally useful salts.

The invention additionally relates to processes for preparing compounds of the formula I, to compositions comprising compounds of the formula I and to the use of these derivatives or to compositions comprising these derivatives for controlling harmful plants.

2-Hetaroylpyrazoles are known from the literature, for example from WO 94/01431 and WO 93/18031.

However, the herbicidal properties of these prior art compounds and their compatibility with crop plants are not entirely satisfactory. It is an object of the present invention to provide novel, in particular herbicidally active, compounds having improved properties.

We have found that this object is achieved by the hetaroyl derivatives of the formula I and their herbicidal action.

Furthermore, the invention provides herbicidal compositions comprising the compounds I and having a very good herbicidal activity. Additionally, the invention provides processes for preparing these compositions and methods for controlling undesirable plant growth using the compounds I.

Depending on the substitution pattern, the compounds of the formula I may contain one or more chiral centers and, if this is the case, be present as enantiomers or as mixtures of diastereomers. The invention provides the pure enantiomers or diastereomers and mixtures thereof.

The compounds of the formula I may also be present in the form of their agriculturally useful salts, the kind of salt generally not being important. The salts of those cations or the acid addition salts of those acids whose cations or anions, respectively, do is not adversely affect the herbicidal activity of the compounds I are generally suitable.

Suitable cations are in particular ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron, and ammonium which may, if desired, carry one to four C₁-C₄-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, and further phosphonium ions and sulfonium ions, preferably tri(C₁-C₄-alkyl)sulfonium and sulfoxonium ions, preferably tri(C₁-C₄-alkyl)sulfoxonium. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C₁-C₄-alkanoic acids, preferably formate, acetate, ropionate and butyrate.

The organic moieties mentioned for the substituents R¹-Rl⁶ or as radicals on phenyl rings represent collective terms for lists of the individual group members. All hydrocarbon chains, ie. all the alkyl, phenylalkyl, phenylcarbonylalkyl, haloalkyl, alkoxy, aloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkoxysulfonyl, haloalkoxysulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkenyl, alkenyloxy, alkenylthio, alkenylsulfinyl, alkenylsulfonyl, alkenyloxysulfonyl, alkynyl, alkynyloxy, alkynylthio, alkynylsulfinyl, alkynylsulfonyl and alkynyloxysulfonyl moieties, ay be straight-chain or branched. Unless stated otherwise, reference is given to halogenated substituents carrying one to five identical or different halogens. Halogen is in each case fluorine, chlorine, bromine or iodine.

Furthermore, the following moieties represent, for example:

C₁-C₄-alkyl and the alkyl moieties of C₁-C₄-alkylcarbonyl, phenyl-C₁-C₄-alkyl and phenylcarbonyl-C₁-C₄-alkyl: methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;

C₁-C₆-alkyl and the alkyl moieties of C₁-C₆-alkylcarbonyl: C₁-C₄-alkyl as mentioned above, and pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-3-methylpropyl;

C₁-C₄-haloalkyl and the haloalkyl moieties of C₁-C₄-haloalkylcarbonyl: a C₁-C₄-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl;

C₁-C₆-haloalkyl and the haloalkyl moieties of C₁-C₆-haloalkylcarbonyl: C₁-C₄-haloalkyl as mentioned above, and 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl and dodecafluorohexyl;

C₁-C₄-alkoxy and the alkoxy moieties in C₁-C₄-alkoxycarbonyl; methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy;

C₁-C₆-alkoxy and the alkoxy moieties in C₁-C₆-alkoxycarbonyl: C₁-C₄-alkoxy as mentioned above, and pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy;

C₁-C₄-haloalkoxy: a C₁-C₄-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3-dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy, 1-(bromomethyl)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy and nonafluorobutoxy;

C₁-C₆-haloalkoxy: C₁-C₄-haloalkoxy as mentioned above, and 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy and dodecafluorohexoxy;

C₁-C₄-alkylthio: methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and 1,1-dimethylethylthio;

C₁-C₆-alkylthio: C₁-C₄-alkylthio as mentioned above, and pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio and 1-ethyl-2-methylpropylthio;

C₁-C₄-haloalkylthio: a C₁-C₄-alkylthio radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. for example fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2,2,2-trichloroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, pentafluoroethylthio, 2-fluoropropylthio, 3-fluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio, 2,3-dichloropropylthio, 3,3,3-trifluoropropylthio, 3,3,3-trichloropropylthio, 2,2,3,3,3-pentafluoropropylthio, heptafluoropropylthio, 1-(fluoromethyl)-2-fluoroethylthio, 1-(chloromethyl)-2-chloroethylthio, 1-(bromomethyl)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio and nonafluorobutylthio;

C₁-C₆-haloalkylthio: C₁-C₄-haloalkylthio as mentioned above, and 5-fluoropentylthio, 5-chloropentylthio, 5-bromopentylthio, 5-iodopentylthio, undecafluoropentylthio, 6-fluorohexylthio, 6-chlorohexylthio, 6-bromohexylthio, 6-iodohexylthio and dodecafluorohexylthio;

C₁-C₄-alkylsulfinyl (C₁-C₄-alkyl-S(=O)—): methylsulfinyl, ethylsulfinyl, propylsulfinyl, 1-methylethylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl and 1,1-dimethylethylsulfinyl;

C₁-C₆-alkylsulfinyl: C₁-C₄-alkylsulfinyl as mentioned above, and pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, 1,1-dimethylpropylsulfinyl, 1,2-dimethylpropylsulfinyl, hexylsulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfinyl, 3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1,1-dimethylbutylsulfinyl, 1,2-dimethylbutylsulfinyl, 1,3-dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3-dimethylbutylsulfinyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl, 1,1,2-trimethylpropylsulfinyl, 1,2,2-trimethylpropylsulfinyl, 1-ethyl-1-methylpropylsulfinyl and 1-ethyl-2-methylpropylsulfinyl;

C₁-C₄-haloalkylsulfinyl: a C₁-C₄-alkylsulfinyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. fluoromethylsulfinyl, difluoromethylsulfinyl, trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethylsulfinyl, 2-fluoroethylsulfinyl, 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl, 2,2-difluoroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl, 2,2,2-trichloroethylsulfinyl, 2-chloro-2-fluoroethylsulfinyl, 2-chloro-2,2-difluoroethylsulfinyl, 2,2-dichloro-2-fluoroethylsulfinyl, pentafluoroethylsulfinyl, 2-fluoropropylsulfinyl, 3-fluoropropylsulfinyl, 2-chloropropylsulfinyl, 3-chloropropylsulfinyl, 2-bromopropylsulfinyl, 3-bromopropylsulfinyl, 2,2-difluoropropylsulfinyl, 2,3-difluoropropylsulfinyl, 2,3-dichloropropylsulfinyl, 3,3,3-trifluoropropylsulfinyl, 3,3,3-trichloropropylsulfinyl, 2,2,3,3,3-pentafluoropropylsulfinyl, heptafluoropropylsulfinyl, 1-(fluoromethyl)-2-fluoroethylsulfinyl, 1-(chloromethyl)-2-chloroethylsulfinyl, 1-(bromomethyl)-2-bromoethylsulfinyl, 4-fluorobutylsulfinyl, 4-chlorobutylsulfinyl, 4-bromobutylsulfinyl and nonafluorobutylsulfinyl;

C₁-C₆-haloalkylsulfinyl: C₁-C₄-haloalkylsulfinyl as mentioned above, and 5-fluoropentylsulfinyl, 5-chloropentylsulfinyl, 5-bromopentylsulfinyl, 5-iodopentylsulfinyl, undecafluoropentylsulfinyl, 6-fluorohexylsulfinyl, 6-chlorohexylsulfinyl, 6-bromohexylsulfinyl, 6-iodohexylsulfinyl and dodecafluorohexylsulfinyl;

C₁-C₄-alkylsulfonyl (C₁-C₄-alkyl-S(=O)₂—): methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl and 1,1-dimethylethylsulfonyl;

C₁-C₆-alkylsulfonyl: C₁-C₄-alkylsulfonyl as mentioned above, is and pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 2,2-dimethylpropylsulfonyl, l-ethylpropylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, n-hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1,l-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl, l-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1,1,2-trimethylpropylsulfonyl, 1,2,2-trimethylpropylsulfonyl, 1-ethyl-1-methylpropylsulfonyl and 1-ethyl-2-methylpropylsulfonyl;

C₁-C₄-haloalkylsulfonyl: a C₁-C₄-alkylsulfonyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl, pentafluoroethylsulfonyl, 2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl, 2-chloropropylsulfonyl, 3-chloropropylsulfonyl, 2-bromopropylsulfonyl, 3-bromopropylsulfonyl, 2,2-difluoropropylsulfonyl, 2,3-difluoropropylsulfonyl, 2,3-dichloropropylsulfonyl, 3,3,3-trifluoropropylsulfonyl, 3,3,3-trichloropropylsulfonyl, 2,2,3,3,3-pentafluoropropylsulfonyl, heptafluoropropylsulfonyl, 1-(fluoromethyl)-2-fluoroethylsulfonyl, 1-(choromethyl)-2-chloroethylsulfonyl, 1-(bromomethyl)-2-bromoethylsulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, 4-bromobutylsulfonyl and nonafluorobutylsulfonyl;

C₁-C₆-haloalkylsulfonyl: C₁-C₄-haloalkylsulfonyl as mentioned above, and 5-fluorbpentylsulfonyl, 5-chloropentylsulfonyl, 5-bromopentylsulfonyl, 5-iodopentylsulfonyl, 6-fluorohexylsulfonyl, 6-bromohexylsulfonyl, 6-iodohexylsulfonyl and didecafluorohexylsulfonyl [sic];

C₁-C₄-alkoxysulfonyl: methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, 1-methylethoxysulfonyl, butoxysulfonyl, 1-methylpropoxysulfonyl, 2-methylpropoxysulfonyl and 1,1-dimethylethoxysulfonyl;

C₁-C₆-alkoxysulfonyl: C₁-C₄-alkoxysulfonyl as mentioned above, and pentoxysulfonyl, 1-methylbutoxysulfonyl, 2-methylbutoxysulfonyl, 3-methylbutoxysulfonyl, 1,1-dimethylpropoxysulfonyl, 1,2-dimethylpropoxysulfonyl, 2,2-dimethylpropoxysulfonyl, 1-ethylpropoxysulfonyl, hexoxysulfonyl, 1-methylpentoxysulfonyl, 2-methylpentoxysulfonyl, 3-methylpentoxysulfonyl, 4-methylpentoxysulfonyl, 1,1-dimethylbutoxysulfonyl, 1,2-dimethylbutoxysulfonyl, 1,3-dimethylbutoxysulfonyl, 2,2-dimethylbutoxysulfonyl, 2,3-dimethylbutoxysulfonyl, 3,3-dimethylbutoxysulfonyl, 1-ethylbutoxysulfonyl, 2-ethylbutoxysulfonyl, 1,1,2-trimethylpropoxysulfonyl, 1,2,2-trimethylpropoxysulfonyl, 1-ethyl-1-methylpropoxysulfonyl and 1-ethyl-2-methylpropoxysulfonyl;

C₁-C₄-haloalkoxysulfonyl: a C₁-C₄-alkoxysulfonyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. for example fluoromethoxysulfonyl, difluoromethoxysulfonyl, trifluoromethoxysulfonyl, chlorodifluoromethoxysulfonyl, bromodifluoromethoxysulfonyl, 2-fluoroethoxysulfonyl, 2-chloroethoxysulfonyl, 2-bromoethoxysulfonyl, 2-iodoethoxysulfonyl, 2,2-difluoroethoxysulfonyl, 2,2,2-trifluoroethoxysulfonyl, 2-chloro-2-fluoroethoxysulfonyl, 2-chloro-2,2-difluoroethoxysulfonyl, 2,2-dichloro-2-fluoroethoxysulfonyl, 2,2,2-trichloroethoxysulfonyl, pentafluoroethoxysulfonyl, 2-fluoropropoxysulfonyl, 3-fluoropropoxysulfonyl, 2-chloropropoxysulfonyl, 3-chloropropoxysulfonyl, 2-bromopropoxysulfonyl, 3-bromopropoxysulfonyl, 2,2-difluoropropoxysulfonyl, 2,3-difluoropropoxysulfonyl, 2,3-dichloropropoxysulfonyl, 3,3,3-trifluoropropoxysulfonyl, 3,3,3-trichloropropoxysulfonyl, 2,2,3,3,3-pentafluoropropoxysulfonyl, heptafluoropropoxysulfonyl, 1-(fluoromethyl)-2-fluoroethoxysulfonyl, 1-(chloromethyl)-2-chloroethoxysulfonyl, 1-(bromomethyl)-2-bromoethoxysulfonyl, 4-fluorobutoxysulfonyl, 4-chlorobutoxysulfonyl, 4-bromobutoxysulfonyl and 4-iodobutoxysulfonyl;

C₁-C₆-haloalkoxysulfonyl: C₁-C₄-haloalkoxysulfonyl as mentioned above, and 5-fluoropentoxysulfonyl, 5-chloropentoxysulfonyl, 5-bromopentoxysulfonyl, 5-iodopentoxysulfonyl, undecafluoropentoxysulfonyl, 6-fluorohexoxysulfonyl, 6-chlorohexoxysulfonyl, 6-bromohexoxysulfonyl, 6-iodohexoxysulfonyl and dodecafluorohexoxysulfonyl;

C₃-C₄-alkenyl, and the alkenyl moieties of C₃-C₄-alkenyloxy, C₃-C₄-alkenylthio, C₃-C₄-alkenylsulfinyl, C₃-C₄-alkenylsulfonyl and C₃-C₄-alkenyloxysulfonyl: prop---en-1-yl, prop-2-en-1-yl, 1-methylethenyl, buten-1-yl, buten-2-yl, buten-3-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl and 2-methylprop-2-en-1-yl;

C₂-C₄-alkenyl, and the alkenyl moieties of C₂-C₄-alkenyloxy, C₂-C₄-alkenylthio, C₂-C₄-alkenylsulfinyl, C₂-C₄-alkenylsulfonyl and C₂-C₄-alkenyloxysulfonyl: C₃-C₄-alkenyl as mentioned above, and ethenyl;

C₃-C₆-alkenyl, and the alkenyl moieties of C₃-C₆-alkenyloxy, C₃-C₆-alkenylthio, C₃-C₆-alkenylsulfinyl, C₂-C₆-alkenylsulfonyl, C₃-C₆-alkenyloxysulfonyl: C₃-C₄-alkenyl as mentioned above, and penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methyl-but-1-en-1-yl, 2-methyl-but-1-en-1-yl, 3-methyl-but-1-en-1-yl, 1-methyl-but-2-en-1-yl, 2-methyl-but-2-en-1-yl, 3-methyl-but-2-en-1-yl, 1-methyl-but-3-en-1-yl, 2-methyl-but-3-en-1-yl, 3-methyl-but-3-en-1-yl, 1,1-dimethyl-prop-2-en-1-yl, 1,2-dimethyl-prop-1-en-1-yl, 1,2-dimethyl-prop-2-en-1-yl, 1-ethyl-prop-1-en-2-yl, 1-ethyl-prop-2-en-1-yl, hex---en-1-yl, hex-2-en-1-yl, hex-3-en-1-yl, hex-4-en-1-yl, hex-5-en-1-yl, 1-methylpent---en-i-yl, 2-methylpent-i-en-1-yl, 3-methylpent-i-en-1-yl, 4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl, 4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl, 1,2-dimethylbut-i-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl, 1,3-dimetylbut-1-en-1-yl, 1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl, 2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl, 1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl, 1-ethyl-2-methylprop-1-en-1-yl and 1-ethyl-2-methylprop-2-en-1-yl;

C₂-C₆-alkenyl and the alkenyl moieties of C₂-C₆-alkenyloxy, C₂-C₆-alkenylthio, C2-C₆-alkenylsulfinyl, C₂-C₆-alkenylsulfonyl, C₂-C₆-alkenyloxysulfonyl: C₃-C₆-alkenyl as mentioned above, and ethenyl;

C₃-C₄-alkynyl and the alkynyl radicals of C₃-C₄-alkynyloxy, C₃-C₄-alkynylthio, C₃-C₄-alkynylsulfinyl, C₃-C₄-alkynylsulfonyl and C₃-C₄-alkynyloxysulfonyl: prop-1-yn-1-yl, prop-2-yn-1-yl, but-1-yn-1-yl, but-1-yn-3-yl, but-1-yn-4-yl and but-2-yn-1-yl;

C₂-C₄-alkynyl, and the alkynyl radicals of C₂-C₄-alkynyloxy, C₂-C₄-alkynylthio, C₂-C₄-alkynylsulfinyl, C₂-C₄-alkynylsulfonyl, C₂-C₄-alkynyloxysulfonyl: C₃-C₆-alkynyl as mentioned above, and ethynyl;

C₃-C₆-alkynyl, and the alkynyl radicals of C₃-C₆-alkynyloxy, C₃-C₆-alkynylthio, C₃-C₆-alkynylsulfinyl, C₃-C₆-alkynylsulfonyl and C₃-C₆-alkynyloxysulfonyl: C₃-C₄-alkynyl as mentioned above, and pent-1-yn-1-yl, pent-1-yn-3-yl, pent-1-yn-4-yl, pent-1-yn-5-yl, pent-2-yn-1-yl, pent-2-yn-4-yl, pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, hex-1-yn-1-yl, hex-1-yn-3-yl, hex-1-yn-4-yl, hex-1-yn-5-yl, hex-1-yn-6-yl, hex-2-yn---yl, hex-2-yn-4-yl, hex-2-yn-5-yl, hex-2-yn-6-yl, hex-3-yn---yl, hex-3-yn-2-yl, 3-methylpent-1-yn-1-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1-yn-5-yl, 4-methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yl and 4-methylpent-2-yn-5-yl;

C₂-C₆-alkynyl, and the alkynyl radicals of C2-C₆-alkynyloxy, C₂-C₆-alkynylthio, C₂-C₆-alkynylsulfinyl, C₂-C₆-alkynylsulfonyl, C₂-C₆-alkynyloxysulfonyl: C₃-C₆-alkynyl as mentioned above, and ethynyl;

All phenyl rings are preferably unsubstituted or carry one to three halogens and/or a nitro group, a cyano radical, or a methyl, trifluoromethyl, methoxy or trif luoromethoxy substituent.

With respect to the use of the compounds of the formula I according to the invention as herbicides, the variables preferably have the meanings below, in each case on their own or in combination:

R¹ is nitro, halogen, hydroxyl, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylsulfonyl, C₁-C₆-haloalkylsulfonyl or phenyl, where the last radical is unsubstituted or may carry one to three halogens and/or a nitro group, a cyano radical, or a methyl, trif luoromethyl, methoxy or trif luoromethoxy substituent; particularly preferably nitro, fluorine, chlorine, bromine, hydroxyl, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, pentafluoroethylsulfonyl or phenyl;

R² is hydrogen, halogen or C₁-C₆-alkyl; particularly preferably hydrogen, chlorine, bromine or methyl;

Z is Z¹, Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸, Z⁹, Z¹⁰, Z¹¹ or Z¹²;

R³, R⁵, R⁷ and R⁹ are each hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, nitro, cyano, hydroxyl, mercapto, C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₂-C₄-alkenyloxy, C₂-C₄-alkynyloxy, C₂-C₄-alkenylthio, C₂-C₄-alkynylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-haloalkylsulfinyl, C₂-C₄-alkenyl-sulfinyl, C₂-C₄-alkynylsulfinyl, C₁-C₄-alkylsulfonyl, C₁-C₄-haloalkylsulfonyl, C₂-C₄-alkenylsulfonyl, C₂-C₄-alkynyl-sulfonyl, C₁-C₄-alkoxysulfonyl, C₁-C₄-haloalkoxysulfonyl, C₂-C₄-alkenyloxysulfonyl, C₂-C₄-alkynyloxysulfonyl, -NR¹²R¹³, —CO₂R¹², —CONR¹²R^(13,) phenyl, phenoxy, phenylthio, phenyl-sulfinyl or phenylaulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following groups: nitro, cyano, hydroxyl, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy; particularly preferably hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, nitro, cyano, hydroxyl, C₁-C₆-alkoxycarbonyl or phenyl, where the last radical is unsubstituted or may carry one to three halogens and/or a nitro group, a cyano radical, or a methyl, trifluoromethyl, methoxy or trifluoromethoxy substituent; especially preferably hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoromethoxy, difluoromethoxy, nitro, cyano, hydroxyl, methoxycarbonyl, ethoxycarbonyl or phenyl;

R⁴, R⁶, R⁸ and R¹⁰ are each hydrogen, halogen or C₁-C₄-alkyl; particularly preferably hydrogen, fluorine, chlorine, methyl or ethyl; especially preferably hydrogen;

R¹¹ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkylcarbonyl, C₁-C₆-haloalkylcarbonyl, C₁-C₆-alkylsulfonyl, C₁-C₆-haloalkylsulfonyl or phenylsulfonyl, where the last phenyl radical may be substituted by a C₁-C₄-alkyl radical; particularly preferably methyl, ethyl, difluoromethyl, trifluoromethyl, methylcarbonyl, ethylcarbonyl, isopropylcarbonyl, trifluoromethylcarbonyl, methylsulfonyl, trifluoromethylsulfonyl, phenylsulfonyl or 4-methylphenylsulfonyl;

R¹² is hydrogen or C₁-C₆-alkyl; particularly preferably hydrogen, methyl or ethyl;

R¹³ is hydrogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₃-C₆-alkenyloxy or C₃-C₆-alkynyloxy; particularly preferably methyl, ethyl, methoxy, ethoxy, 2-propen-1-yloxy, 2-propyn-1-yloxy or 1-methyl-2-propyn-1-yloxy;

R¹⁴ is C₁-C₆-alkyl or C₁-C₆-haloalkyl; particularly preferably methyl, ethyl, propyl, isopropyl, butyl or isobutyl;

R¹⁵ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkyl-carbonyl, C₁-C₆-haloalkylcarbonyl, C₁-C₆-alkoxycarbonyl, C₁-C₆-alkylsulfonyl, C₁-C₆-haloalkylsulfonyl, phenylcarbonyl, phenoxycarbonyl or phenylsulfonyl, where the last three substituents may be partially or fully halogenated and may carry one to three of the following radicals: nitro, cyano, cl-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy; particularly preferably hydrogen, C₁-C₆-alkyl, C₁-C₆-alkyl-carbonyl, C₁-Cf-haloalkylcarbonyl, C₁-C6-alkoxycarbonyl, C₁-C₆-alkylsulfonyl, C₁-C₆-haloalkylsulfonyl or phenyl-sulfonyl, where the phenyl ring of the last substituent may be partially or fully halogenated and may carry one to three of the following radicals: nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy;

R¹⁶ is hydrogen, C₁-C₆-alkyl or C₁-C₆-haloalkyl; particularly preferably hydrogen, methyl, ethyl or trifluoromethyl.

Preference is given to compounds of the formula I where the variable Z is Z¹, Z², Z¹¹ or Z¹², especially Z¹ or Z².

Likewise preferred are compounds of the formula I where the variable Z is Z³, Z⁴, Z⁵, Z⁶, Z⁷ or Z⁸, especially Z³, Z⁵, Z⁶, Z⁷ or Z⁸.

Likewise preferred are the compounds of the formula I where the variable z is z⁹ or Z¹⁰.

Particular preference is given to compounds of the formulae Ia-Ic (Z=Z¹) and Id—Ie (Z=Z²) and their N-oxides Ia′-Ic′ (Z=Z¹¹) and Id′-Ie′ (Z=Z¹²) and particular preference is also given to compounds of the formulae If (Z=Z⁹) and Ig (z=Z¹⁰).

Futhemor, preference is given to the compounds Ia, Ib, Ic, Id and Ie. Likewise, preference is given to the compounds If and Ig where CR³R⁴, CR⁵R⁶, CR⁷R⁸ and/or CR⁹R¹⁰ may not be replaced by C=O or C=NR¹³.

Furthermore, preference is given to the compounds If where CR⁵R⁶ is replaced by C=O or C=NR¹³ and to the compounds Ig where CR⁷R⁸ is replaced by C=o or C=NR¹³.

Very particular preference is given to the compounds Ial ({circumflex over (=)} I where R², R¹⁵ and R¹⁶=H and R¹⁴=CH₃ and where the “Q—CO—fragment” is attached in position a, R¹ is attached in position d and Z¹ is attached in positions b and c) listed in Table 1.

TABLE 1 No. R¹ R⁵ R⁷ R⁹ Ia1.001 Br H H H Ia1.002 Cl H H H Ia1.003 SO₂CH₃ H H H Ia1.004 CH₃ H H H Ia1.005 OH H H H Ia1.006 OCH₃ H H H Ia1.007 CF₃ H H H Ia1.008 NO₂ H H H Ia1.009 F H H H Ia1.010 OCF₃ H H H Ia1.011 C₆H₅ H H H Ia1.012 Br H CH₃ H Ia1.013 Cl H CH₃ H Ia1.014 SO₂CH₃ H CH₃ H Ia1.015 CH₃ H CH₃ H Ia1.016 OH H CH₃ H Ia1.017 OCH₃ H CH₃ H Ia1.018 CF₃ H CH₃ H Ia1.019 NO₂ H CH₃ H Ia1.020 F H CH₃ H Ia1.021 OCF₃ H CH₃ H Ia1.022 C₆H₅ H CH₃ H Ia1.023 Br CH₃ H H Ia1.024 Cl CH₃ H H Ia1.025 SO₂CH₃ CH₃ H H Ia1.026 CH₃ CH₃ H H Ia1.027 OH CH₃ H H Ia1.028 OCH₃ CH₃ H H Ia1.029 CF₃ CH₃ H H Ia1.030 NO₂ CH₃ H H Ia1.031 F CH₃ H H Ia1.032 OCF₃ CH₃ H H Ia1.033 C₆H₅ CH₃ H H Ia1.034 Br H H CH₃ Ia1.035 Cl H H CH₃ Ia1.036 SO₂CH₃ H H CH₃ Ia1.037 CH₃ H H CH₃ Ia1.038 OH H H CH₃ Ia1.039 OCH₃ H H CH₃ Ia1.040 CF₃ H H CH₃ Ia1.041 NO₂ H H CH₃ Ia1.042 F H H CH₃ Ia1.043 OCF₃ H H CH₃ Ia1.044 C₆H₅ H H CH₃ Ia1.045 Br CH₃ CH₃ CH₃ Ia1.046 Cl CH₃ CH₃ CH₃ Ia1.047 SO₂CH₃ CH₃ CH₃ CH₃ Ia1.048 CH₃ CH₃ CH₃ CH₃ Ia1.049 OH CH₃ CH₃ CH₃ Ia1.050 OCH₃ CH₃ CH₃ CH₃ Ia1.051 CF₃ CH₃ CH₃ CH₃ Ia1.052 NO₂ CH₃ CH₃ CH₃ Ia1.053 F CH₃ CH₃ CH₃ Ia1.054 OCF₃ CH₃ CH₃ CH₃ Ia1.055 C₆H₅ CH₃ CH₃ CH₃ Ia1.056 Br H Cl H Ia1.057 Cl H Cl H Ia1.058 SO₂CH₃ H Cl H Ia1.059 CH₃ H Cl H Ia1.060 OH H Cl H Ia1.061 OCH₃ H Cl H Ia1.062 CF₃ H Cl H Ia1.063 NO₂ H Cl H Ia1.064 F H Cl H Ia1.065 OCF₃ H Cl H Ia1.066 C₆H₅ H Cl H Ia1.067 Br Cl H H Ia1.068 Cl Cl H H Ia1.069 SO₂CH₃ Cl H H Ia1.070 CH₃ Cl H H Ia1.071 OH Cl H H Ia1.072 OCH₃ Cl H H Ia1.073 CF₃ Cl H H Ia1.074 NO₂ Cl H H Ia1.075 F Cl H H Ia1.076 OCF₃ Cl H H Ia1.077 C₆H₅ Cl H H Ia1.078 Br H H Cl Ia1.079 Cl H H Cl Ia1.080 SO₂CH₃ H H Cl Ia1.081 CH₃ H H Cl Ia1.082 OH H H Cl Ia1.083 OCH₃ H H Cl Ia1.084 CF₃ H H Cl Ia1.085 NO₂ H H Cl Ia1.086 F H H Cl Ia1.087 OCF₃ H H Cl Ia1.088 C₆H₅ H H Cl Ia1.089 Br Cl Cl Cl Ia1.090 Cl Cl Cl Cl Ia1.091 SO₂CH₃ Cl Cl Cl Ia1.092 CH₃ Cl Cl Cl Ia1.093 OH Cl Cl Cl Ia1.094 OCH₃ Cl Cl Cl Ia1.095 CF₃ Cl Cl Cl Ia1.096 NO₂ Cl Cl Cl Ia1.097 F Cl Cl Cl Ia1.098 OCF₃ Cl Cl Cl Ia1.099 C₆H₅ Cl Cl Cl Ia1.100 Br C₆H₅ H H Ia1.101 Cl C₆H₅ H H Ia1.102 SO₂CH₃ C₆H₅ H H Ia1.103 CH₃ C₆H₅ H H Ia1.104 OH C₆H₅ H H Ia1.105 OCH₃ C₆H₅ H H Ia1.106 CF₃ C₆H₅ H H Ia1.107 NO₂ C₆H₅ H H Ia1.108 F C₆H₅ H H Ia1.109 OCF₃ C₆H₅ H H Ia1.110 C₆H₅ C₆H₅ H H Ia1.111 Br CH₃ OH H Ia1.112 Cl CH₃ OH H Ia1.113 SO₂CH₃ CH₃ OH H Ia1.114 CH₃ CH₃ OH H Ia1.115 OH CH₃ OH H Ia1.116 OCH₃ CH₃ OH H Ia1.117 CF₃ CH₃ OH H Ia1.118 NO₂ CH₃ OH H Ia1.119 F CH₃ OH H Ia1.120 OCF₃ CH₃ OH H Ia1.121 C₆H₅ CH₃ OH H Ia1.122 Br CF₃ H H Ia1.123 Cl CF₃ H H Ia1.124 SO₂CH₃ CF₃ H H Ia1.125 CH₃ CF₃ H H Ia1.126 OH CF₃ H H Ia1.127 OCH₃ CF₃ H H Ia1.128 CF₃ CF₃ H H Ia1.129 NO₂ CF₃ H H Ia1.130 F CF₃ H H Ia1.131 OCF₃ CF₃ H H Ia1.132 C₆H₅ CF₃ H H Ia1.133 Br CH₃ H OH Ia1.134 Cl CH₃ H OH Ia1.135 SO₂CH₃ CH₃ H OH Ia1.136 CH₃ CH₃ H OH Ia1.137 OH CH₃ H OH Ia1.138 OCH₃ CH₃ H OH Ia1.139 CF₃ CH₃ H OH Ia1.140 NO₂ CH₃ H OH Ia1.141 F CH₃ H OH Ia1.142 OCF₃ CH₃ H OH Ia1.143 C₆H₅ CH₃ H OH Ia1.144 Br H H OCH₃ Ia1.145 Cl H H OCH₃ Ia1.146 SO₂CH₃ H H OCH₃ Ia1.147 CH₃ H H OCH₃ Ia1.148 OH H H OCH₃ Ia1.149 OCH₃ H H OCH₃ Ia1.150 CF₃ H H OCH₃ Ia1.151 NO₂ H H OCH₃ Ia1.152 F H H OCH₃ Ia1.153 H H H OCH₃ Ia1.154 OCF₃ H H OCH₃ Ia1.155 C₆H₅ H H OCH₃ Ia1.156 Br Cl Cl CH₃ Ia1.157 Cl Cl Cl CH₃ Ia1.158 SO₂CH₃ Cl Cl CH₃ Ia1.159 CH₃ Cl Cl CH₃ Ia1.160 OH Cl Cl CH₃ Ia1.161 OCH₃ Cl Cl CH₃ Ia1.162 CF₃ Cl Cl CH₃ Ia1.163 NO₂ Cl Cl CH₃ Ia1.164 F Cl Cl CH₃ Ia1.165 OCF₃ Cl Cl CH₃ Ia1.166 C₆H₅ Cl Cl CH₃ Ia1.167 Br CF₃ H Br Ia1.168 Cl CF₃ H Br Ia1.169 SO₂CH₃ CF₃ H Br Ia1.170 CH₃ CF₃ H Br Ia1.171 OH CF₃ H Br Ia1.172 OCH₃ CF₃ H Br Ia1.173 CF₃ CF₃ H Br Ia1.174 NO₂ CF₃ H Br Ia1.175 F CF₃ H Br Ia1.176 H CF₃ H Br Ia1.177 OCF₃ CF₃ H Br Ia1.178 C₆H₅ CF₃ H Br Ia1.179 Br OH CN H Ia1.180 Cl OH CN H Ia1.181 SO₂CH₃ OH CN H Ia1.182 CH₃ OH CN H Ia1.183 OH OH CN H Ia1.184 OCH₃ OH CN H Ia1.185 CF₃ OH CN H Ia1.186 NO₂ OH CN H Ia1.187 F OH CN H Ia1.188 OCF₃ OH CN H Ia1.189 C₆H₅ OH CN H Ia1.190 Br H CF₃ H Ia1.191 Cl H CF₃ H Ia1.192 SO₂CH₃ H CF₃ H Ia1.193 CH₃ H CF₃ H Ia1.194 OH H CF₃ H Ia1.195 OCH₃ H CF₃ H Ia1.196 CF₃ H CF₃ H Ia1.197 NO₂ H CF₃ H Ia1.198 F H CF₃ H Ia1.199 OCF₃ H CF₃ H Ia1.200 C₆H₅ H CF₃ H Ia1.201 Br H H NO₂ Ia1.202 Cl H H NO₂ Ia1.203 SO₂CH₃ H H NO₂ Ia1.204 CH₃ H H NO₂ Ia1.205 OH H H NO₂ Ia1.206 OCH₃ H H NO₂ Ia1.207 CF₃ H H NO₂ Ia1.208 NO₂ H H NO₂ Ia1.209 F H H NO₂ Ia1.210 OCF₃ H H NO₂ Ia1.211 C₆H₅ H H NO₂

Furthermore, very particular preference is given to the following hetaroyl derivatives of the formula I:

the compounds Ia2.001-Ia2.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl:

the compounds Ia3.001-Ia3.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that R¹⁵ is methyl:

the compounds Ia4.001-Ia4.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is methyl:

the compounds Ia5.001-Ia5.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that R¹⁵ is ethyl:

the compounds Ia6.001-Ia6.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that R¹⁴ and R¹⁵ are each ethyl:

the compounds Ia7.001-Ia7.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that R¹⁵ is n-propyl:

the compounds Ia8.001-Ia8.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is n-propyl:

the compounds Ia9.001-Ia9.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-butyl:

the compounds Ia10.001-Ia10.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is n-butyl:

the compounds Ia11.001-Ia11.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is methylcarbonyl:

the compounds Ia12.001-Ia12.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is methylcarbonyl:

the compounds Ia13.001-Ia13.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is ethylcarbonyl:

the compounds Ia14.001-Ia14.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is ethylcarbonyl:

the compounds Ia15.001-Ia15.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-propylcarbonyl:

the compounds Ia1.6.001-Ia16.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is n-propylcarbonyl:

the compounds Ia17.001-Ia17.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-butylcarbonyl:

the compounds Ia18.001-Ia18.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is n-butylcarbonyl:

the compounds Ia19.001-Ia19.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is trifluoromethylcarbonyl:

the compounds Ia20.001-Ia20.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is trifluorocarbonyl:

the compounds Ia21.001-Ia21.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is methylsulfonyl:

the compounds Ia22.001-Ia22.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is methylsulfonyl:

the compounds Ia23.001-Ia23.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is ethylsulfonyl:

the compounds Ia24.001-Ia24.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is ethylsulfonyl:

the compounds Ia25.001-Ia25.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-propylsulfonyl:

the compounds Ia26.001-Ia26.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is n-propylsulfonyl:

the compounds Ia27.001-Ia27.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-butylsulfonyl:

the compounds Ia28.001-Ia28.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is n-butylsulfonyl:

the compounds Ia29.001-Ia29.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is triofluoromethylsulfonyl:

the compounds Ia30.001-Ia30.211, which differ from the compounds Ia001-Ia211 in that R¹⁴ is ethyl and R¹⁵ is trifluoromethylsulfonyl:

the compounds Ia31.001-Ia31.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is phenylsulfonyl:

the compounds Ia32.001-Ia32.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is phenylsulfonyl:

the compounds Ia33.001-Ia33.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is 4-methylphenylsulfonyl:

the compounds Ia34.001-Ia34.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is 4-methylphenylsulfonyl:

the compounds Ia35.001-Ia35.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁶ is methyl:

the compounds Ia36.001-Ia36.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁶ is methyl:

the compounds Ia37.001-Ia37.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ and R¹⁶ are each methyl:

the compounds Ia38.001-Ia38.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ and R¹⁶ are each methyl:

the compounds Ia39.001-Ia39.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is ethyl and R¹⁶ is methyl:

the compounds Ia40.001-Ia40.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ and R¹⁵ are each ethyl and R¹⁶ is methyl:

the compounds Ia41.001-Ia41.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-propyl and R¹⁶ is methyl:

the compounds Ia42.001-Ia42.211, which differ from the compounds Ia001-Ia211 in that R¹⁴ is ethyl, R¹⁵ is n-propyl and R¹⁶ is methyl:

the compounds Ia43.001-Ia43.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-butyl and R¹⁶ is methyl:

the compounds Ia44.001-Ia44.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is n-butyl and R¹⁶ is methyl:

the compounds Ia45.001-Ia45.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is methylcarbonyl and R¹⁶ is methyl:

the compounds Ia46.001-Ia46.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is methylcarbonyl and R¹⁶ is methyl:

the compounds Ia47.001-Ia47.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is ethylcarbonyl and R¹⁶ is methyl:

the compounds Ia48.001-Ia48.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is ethylcarbonyl and R¹⁶ is methyl:

the compounds Ia49.001-Ia49.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-propylcarbonyl and R¹⁶ is methyl:

the compounds Ia50.001-Ia50.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is n-propylcarbonyl and R¹⁶ is methyl:

the compounds Ia51.001-Ia51.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-butylcarbonyl and R¹⁶ is methyl:

the compounds Ia52.001-Ia52.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is n-butylcarbonyl and R¹⁶ is methyl:

the compounds Ia53.001-Ia53.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is trif luoromethylcarbonyl and R¹⁶ is methyl:

the compounds Ia54.001-Ia54.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is trifluoromethylcarbonyl and R¹⁶ is methyl:

the compounds Ia55.001-Ia55.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is methylsulfonyl and R¹⁶ is methyl:

the compounds la56.001-Ia56.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is methylsulfonyl and R¹⁶ is methyl:

the compounds Ia57.001-Ia57.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is ethylsulfonyl and R¹⁶ is methyl:

the compounds Ia58.001-Ia58.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is ethylsulfonyl and R¹⁶ is methyl:

the compounds Ia59.01-Ia59.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-propylsulfonyl and R¹⁶ is methyl:

the compounds Ia60.001-Ia60.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is n-propylsulfonyl and R¹⁶ is methyl:

the compounds Ia61.001-Ia61.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-butylsulfonyl and R¹⁶ is methyl:

the compounds Ia62.001-Ia62.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is n-butylsulfonyl and R¹⁶ is methyl:

the compounds Ia63.001-Ia63.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is trifluoromethylsulfonyl and R¹⁶ is methyl:

the compounds Ia64.001-Ia64.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is trifluoromethylsulfonyl and R¹⁶ is methyl:

the compounds Ia65.001-Ia65.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is phenylsulfonyl and R¹⁶ is methyl:

the compounds Ia66.001-Ia66.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is phenylsulfonyl and R¹⁶ is methyl:

the compounds Ia67.001-Ia67.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is 4-methylphenylsulfonyl and R¹⁶ is methyl:

the compounds Ia68.001-Ia68.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is 4-methylphenylsulfonyl and R¹⁶ is methyl:

the compounds Ia′1-001-Ia′1.211, which differ from the compounds Ia1.001-Ia1.211 in that they are the N-oxides (z=Z¹¹):

the compounds Ia′2-001-Ia′2.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′3.001-Ia′3.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′4.001-Ia′4.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′5.001-Ia′5.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is ethyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′6.001-Ia′6.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ and R¹⁵ are each ethyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′7.001-Ia′7.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-propyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′8.001-Ia′8.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is n-propyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′9.001-Ia′9.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-butyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′10.001-Ia′10.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is n-butyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′11.001-Ia′11.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is methylcarbonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′12.001-Ia′12.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is methylcarbonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′13.001-Ia′13.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is ethylcarbonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′14.001-Ia′14.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is ethylcarbonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′15.001-Ia′15.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-propylcarbonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′16.001-Ia′16.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is n-propylcarbonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′17.001-Ia′17.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-butylcarbonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′18.001-Ia′18.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is n-butylcarbonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′19.001-Ia′19.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is trifluoromethylcarbonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′20.001-Ia′20.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is trifluoromethylcarbonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′21.001-Ia′21.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is methylsulfonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′22.001-Ia′22.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is methylsulfonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′23.001-Ia′23.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is ethylsulfonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′24.001-Ia′24.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is ethylsulfonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′25.001-Ia′25.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-propylsulfonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′26.001-Ia′26.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is n-propylsulfonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′27.001-Ia′27.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-butylsulfonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′28.001-Ia′28.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is n-butylsulfonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′29.001-Ia′29.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is trifluoromethylsulfonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′30.001-Ia′30.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is trifluoromethylsulfonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′31.001-Ia′31.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is phenylsulfonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′32.001-Ia′32.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is phenylsulfonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′33.001-Ia′33.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is 4-methylphenylsulfonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′34.001-Ia′34.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁵ is 4-methylphenylsulfonyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′35.001-Ia′35.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′36.001-Ia′36.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′37.001-Ia′37.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ and R¹⁶ are each methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′38.001-Ia′38.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ and R¹⁶ are each methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′39.001-Ia′39.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is ethyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹)

the compounds Ia′40.001-Ia′40.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ and R¹⁵ are each ethyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′41.001-Ia′41.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-propyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′42.001-Ia′42.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is n-propyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′43.001-Ia′43.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-butyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′44.001-Ia′44.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is n-butyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′45.001-Ia′45.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is methylcarbonyl and R¹⁶ is methyl and in that they are the N-oxides (z=Z¹¹):

the compounds Ia′46.001-Ia′46.2111, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is methylcarbonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′47.001-Ia′47.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is ethylcarbonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′48.001-Ia′48.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is ethylcarbonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′49.001-Ia′49.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-propylcarbonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′50.001-Ia′50.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is n-propylcarbonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′51.001-Ia′51.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-butylcarbonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′52.001-Ia′52.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is n-butylcarbonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′53.001-Ia′53.211, which differ from the compounds Ia001-Ia211 in that R¹⁵ is trifluoromethylcarbonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′54.001-Ia′54.211, which differ from the compounds Ia1.001-Ia211 in that R¹⁴ is ethyl, R¹⁵ is trifluoromethylcarbonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′55.001-Ia′55.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is methylsulfonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′56.001-Ia′56.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is methylsulfonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′57.001-Ia′57.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is ethylsulfonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′58.001-Ia′58.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is ethylsulfonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′59.001-Ia′59.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-propylsulfonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′60.001-Ia′60.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is n-propylsulfonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′61.001-Ia′61.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is n-butylsulfonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′62.001-Ia′62.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is n-butylsulfonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′63.001-Ia′63.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is trifluoromethylsulfonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′64.001-Ia′64.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is trifluoromethylsulfonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′65.001-Ia′65.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is phenylsulfonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′66.001-Ia′66.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is phenylsulfonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′67.001-Ia′67.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁵ is 4-methylphenylsulfonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

the compounds Ia′68.001-Ia′68.211, which differ from the compounds Ia1.001-Ia1.211 in that R¹⁴ is ethyl, R¹⁵ is 4-methylphenylsulfonyl and R¹⁶ is methyl and in that they are the N-oxides (Z=Z¹¹):

Likewise, very particular preference is given to the compounds Ib1({circumflex over (=)} I where R¹⁴ CH₃ and R¹⁵=H and where the “Q—CO— fragment” is attached in position e, RI is attached in position d, R² is attached in position a and Z¹ is attached in positions b and c) listed in Table 2 below.

TABLE 2 No. R¹ R² R⁵ R⁷ R⁹ Ib1.01 CH₃ H H H H Ib1.02 CH₃ H H H CH₃ Ib1.03 CH₃ H H CH₃ H Ib1.04 CH₃ H CH₃ H H Ib1.05 CH₃ CH₃ H H H Ib1.06 CH₃ H H H Cl Ib1.07 CH₃ H H Cl H Ib1.08 CH₃ H Cl H H Ib1.09 CH₃ Cl H H H Ib1.10 CH₃ H H H CF₃ Ib1.11 CH₃ H H CF₃ H Ib1.12 CH₃ H CF₃ H H Ib1.13 Cl H H H H Ib1.14 Cl H H H CH₃ Ib1.15 Cl H H CH₃ H Ib1.16 Cl H CH₃ H H Ib1.17 Cl H H H Cl Ib1.18 Cl H H Cl H Ib1.19 Cl H Cl H H Ib1.20 Cl H Cl Cl Cl Ib1.21 CH₃ H CH₃ CH₃ CH₃

Furthermore, very particular preference is given to the following hetaroyl derivatives of the formula I:

the compounds Ib2.01-Ib2.21, which differ from the corresponding compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl:

the compounds Ib3.01-Ib3.21 which differ from the corresponding compounds Ib1.01-Ib1.21 in that R¹⁵ is methyl:

the compounds Ib4.01-Ib4.21, which differ from the corresponding compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl and R¹⁵ is methyl:

the compounds Ib5.01-Ib5.21, which differ from the corresponding compounds Ib1.01-Ib1.21 in that R¹⁵ is ethyl:

the compounds Ib6.01-Ib6.21, which differ from the corresponding compounds Ib1.01 -Ib1.21 in that R¹⁴ and R¹⁵ are ehyl:

the compounds Ib7.01-Ib7.21, which differ from the corresponding compounds Ib1.01-Ib1.21 in that R¹⁵ is n-propyl:

the compounds Ib8.01-Ib8.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl and R¹⁵ is n-propyl:

the compounds Ib9.01-Ib9.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is n-butyl:

the compounds Ib11.01-Ib11.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl and R¹⁵ is n-butyl:

the compounds Ib11.01-Ib11.21 which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is methylcarbonyl:

the compounds Ib12.01-Ib12.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl and R¹⁵ is methylcarbonyl:

the compounds Ib13.01-Ib13.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is ethylcarbonyl:

the compounds Ib14.01-Ib14.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl and R¹⁵ is ethylcarbonyl:

the compounds Ib15.01-IbI5.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is n-propylcarbonyl:

the compounds Ib16.01-Ib16.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl and R¹⁵ is n-propylcarbonyl:

the compounds Ib17.01-Ib17.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is n-butylcarbonyl:

the compounds Ib18.01-Ib18.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl and R¹⁵ is n-butylcarbonyl:

the compounds Ib19.01-Ib19.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is trifluoromethylcarbonyl:

the compounds Ib20.01-Ib20.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl and R¹⁵ is trifluorocarbonyl:

the compounds Ib21.01-Ib21.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is methylsulfonyl:

the compounds Ib22.01-Ib22.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl and R¹⁵ is methylsulfonyl:

the compounds Ib23.01-Ib23.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is ethylsulfonyl:

the compounds Ib24.01-Ib24.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl and R¹⁵ is ethylsulfonyl:

the compounds Ib25.01-Ib25.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is n-propylsulfonyl:

the compounds Ib26.01-Ib26.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl and R¹⁵ is n-propylsulfonyl:

the compounds Ib27.01-Ib27.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is n-butylsulfonyl:

the compounds Ib28.01-Ib28.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl and R¹⁵ is n-butylsulfonyl:

the compounds Ib29.01-Ib29.21, which differ from the Icompounds Ib1.01-Ib1.21 in that R¹⁵ is trifluoromethylsulfonyl:

the compounds Ib30.01-Ib30.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl and R¹⁵ is trifluoromethylsulfonyl:

the compounds Ib31.01-Ib31.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is phenylsulfonyl:

the compounds Ib32.01-Ib32.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl and R¹⁵ is phenylsulfonyl:

the compounds Ib33.01-Ib33.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is 4-methylphenylsulfonyl:

the compounds Ib34.01-Ib34.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl and R¹⁵ is 4-methylphenylsulfonyl:

the compounds Ib35.01-Ib35.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁶ is methyl:

the compounds Ib36.01-Ib36.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl and R¹⁶ is methyl:

the compounds Ib37.01-Ib37.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ and R¹⁶ are each methyl:

the compounds Ib38.01-Ib38.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl and R¹⁵ and R¹⁶ are each methyl:

the compounds Ib39.01-Ib39.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is ethyl and R¹⁶ is methyl:

the compounds Ib40.01-Ib40.21, which differ from the compounds Ib1.01-Ib1.21 in that R14 and R¹⁵ are each ethyl and R¹⁶ is methyl:

the compounds Ib41.01-Ib41.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is n-propyl and R¹⁶ is methyl:

the compounds Ib42.01-Ib42.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl, R¹⁵ is n-propyl and R¹⁶ is methyl:

the compounds Ib43.01-Ib43.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is n-butyl and R¹⁶ is methyl:

the compounds Ib44.01-Ib44.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl, R¹⁵ is n-butyl and R¹⁶ is methyl:

the compounds Ib45.01-Ib45.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is methylcarbonyl and R¹⁶ is methyl:

the compounds Ib46.01-Ib46.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl, R¹⁵ is methylcarbonyl and R¹⁶ is methyl:

the compounds Ib47.01-Ib47.21, which differ from the compounds Ib01-Ib21 in that R¹⁵ is ethylcarbonyl and R¹⁶ is methyl:

the compounds Ib48.01-Ib48.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl, R¹⁵ is ethylcarbonyl and R¹⁶ is methyl:

the compounds Ib49.01-Ib49.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is n-propylcarbonyl and R¹⁶ is methyl:

the compounds Ib50.01-Ib50.21, which differ from the corresponding compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl, R¹⁵ is n-propylcarbonyl and R¹⁶ is methyl:

the compounds Ib51.01-Ib51.21, which differ from the compounds Ib1.001-Ib1.211 [sic] in that R¹⁵ is n-butylcarbonyl and R¹⁶ is methyl:

the compounds Ib52.01-Ib52.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl, R¹⁵ is n-butylcarbonyl and R¹⁶ is methyl:

the compounds Ib53.01-Ib53.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is trifluoromethylcarbonyl and R¹⁶ is methyl:

the compounds Ib54.01-Ib54.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl, R¹⁵ is trifluoromethylcarbonyl and R¹⁶ is methyl:

the compounds Ib55.01-Ib55.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is methylsulfonyl and R¹⁶ is methyl:

the compounds Ib56.01-Ib56.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl, R¹⁵ is methylsulfonyl and R¹⁶ is methyl:

the compounds Ib57.01-Ib57.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is ethylsulfonyl and R¹⁶ is methyl:

the compounds Ib58.O1-Ib58.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl, R¹⁵ is ethsulfonyl and R¹⁶ is methyl:

the compounds Ib59.01-Ib59.21, which differ from the compounds Ib01-Ib21 in that R¹⁵ is n-propylsulfonyl and R¹⁶ is methyl:

the compounds Ib60.01-Ib60.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl, R¹⁵ is n-propylsulfonyl and R¹⁶ is methyl:

the compounds Ib61.01-Ib61.21, which differ from the compounds Ib01-Ib21 in that R¹⁵ is n-butylsulfonyl and R¹⁶ is methyl:

the compounds Ib62.01-Ib62.21, which differ from the compounds Ib01-Ib21 in that R¹⁴ is ethyl, R¹⁵ is n-butylsulfonyl and R¹⁶ is methyl:

the compounds lb63.01-Ib63.21, which differ from the compounds Ib01-Ib21 in that R¹⁵ is trifluoromethylsulfonyl and R¹⁶ is methyl:

the compounds Ib64.01-Ib64.21, which differ from the compounds Ib01-Ib21 in that R¹⁴ is ethyl, R¹⁵ is trifluoromethylsulfonyl and R¹⁶ is methyl:

the compounds Ib65.01-Ib65.21, which differ from the compounds Ib01-Ib21 in that R¹⁵ is phenylsulfonyl and R¹⁶ is methyl:

the compounds Ib66.01-Ib66.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl, R¹⁵ is phenylsulfonyl and R¹⁶ is methyl:

the compounds Ib67.01-Ib67.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁵ is 4-methylphenylsulfonyl and R¹⁶ is methyl:

the compounds Ib68.01-Ib68.21, which differ from the compounds Ib1.01-Ib1.21 in that R¹⁴ is ethyl, R¹⁵ is 4-methylphenylsulfonyl and R¹⁶ is methyl:

In addition, very particular preference is given to the compounds Ic1 ({circumflex over (=)} I where R², R¹⁵, R¹⁶=H and R¹⁴=CH₃ and where the “Q-CO-fragment” is attached in position d, R¹ is attached in position a and Z¹ is attached in positions b and c) listed in Table 3 below:

TABLE 3 No. R¹ R⁵ R⁷ R⁹ Ic1.01 Br CH₃ H H Ic1.02 Cl CH₃ H H Ic1.03 SO₂CH₃ CH₃ H H Ic1.04 CH₃ CH₃ H H Ic1.05 OH CH₃ H H Ic1.06 OCH₃ CH₃ H H Ic1.07 CF₃ CH₃ H H Ic1.08 NO₂ CH₃ H H Ic1.09 F CH₃ H H Ic1.10 OCF₃ CH₃ H H Ic1.11 C₆H₅ CH₃ H H Ic1.12 Br CF₃ H H Ic1.13 Cl CF₃ H H Ic1.14 SO₂CH₃ CF₃ H H Ic1.15 CH₃ CF₃ H H Ic1.16 OH CF₃ H H Ic1.17 OCH₃ CF₃ H H Ic1.18 CF₃ CF₃ H H Ic1.19 NO₂ CF₃ H H Ic1.20 F CF₃ H H Ic1.21 OCF₃ CF₃ H H Ic1.22 C₆H₅ CF₃ H H Ic1.23 Br H H H Ic1.24 Cl H H H Ic1.25 SO₂CH₃ H H H Ic1.26 CH₃ H H H Ic1.27 OH H H H Ic1.28 OCH₃ H H H Ic1.29 CF₃ H H H Ic1.30 NO₂ H H H Ic1.31 F H H H Ic1.32 OCF₃ H H H Ic1.33 C₆H₅ H H H Ic1.34 Br Cl H H Ic1.35 Cl Cl H H Ic1.36 SO₂CH₃ Cl H H Ic1.37 CH₃ Cl H H Ic1.38 OH Cl H H Ic1.39 OCH₃ Cl H H Ic1.40 CF₃ Cl H H Ic1.41 NO₂ Cl H H Ic1.42 F Cl H H Ic1.43 OCF₃ Cl H H Ic1.44 C₆H₅ Cl H H

Furthermore, very particular preference is given to the following hetaroyl derivatives of the formula I:

the compounds Ic2.01-Ic2.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl:

the compounds Ic3.01-Ic3.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is methyl:

the compounds Ic4.01-Ic4.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl and R¹⁵ is methyl:

the compounds Ic5.01-Ic5.44, which differ from the corresponding compounds Ic1.01-Ic1.44 in that R¹⁵ is ethyl:

the compounds Ic6.01-Ic6.44, which differ from the corresponding compounds Ic1.01-Ic1.44 in that R¹⁴ and R¹⁵ are each ethyl:

the compounds Ic7.01-Ic7.44, which differ from the corresponding compounds Ic1.01-Ic1.44 in that R¹⁵ is n-propyl:

the compounds Ic8.01-Ic8.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl and R¹⁵ is n-propyl:

the compounds Ic9.01-Ic9.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is n-butyl:

the compounds Ic10.01-Ic10.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl and R¹⁵ is n-butyl:

the compounds Ic11.01-Ic11.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is methylcarbonyl:

the compounds Ic12.01-Ic12.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl and R¹⁵ is methylcarbonyl:

the compounds Ic1.01-Ic1.44 in that R¹⁵ is ethylcarbonyl:

the compounds Ic14.01-Ic14.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl and R¹⁵ is ethylcarbonyl:

the compounds Ic15.01-Ic15.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is n-propylcarbonyl:

the compounds Ic16.01-Ic16.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl and R¹⁵ is n-propylcarbonyl:

the compounds Ic17.01-Ic17.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is n-butylcarbonyl:

the compounds Ic18.01-Ic18.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl and R¹⁵ is n-butylcarbonyl:

the compounds Ic19.01-Ic19.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is trifluoromethylcarbonyl:

the compounds Ic20.01-Ic20.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl and R¹⁵ is trifluoromethylcarbonyl:

the compounds Ic21.01-Ic21.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is methylsulfonyl:

the compounds Ic22.01-Ic22.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl and R¹⁵ is methylsulfonyl:

the compounds Ic23.01-Ic23.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is ethylsulfonyl:

the compounds Ic24.01-Ic24.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl and R¹⁵ is ethylsulfonyl:

the compounds Ic25.01-Ic25.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is n-propylsulfonyl:

the compounds Ic26.01-Ic26.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl and R¹⁵ is n-propylsulfonyl:

the compounds Ic27.01-Ic27.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is n-butylsulfonyl:

the compounds Ic28.01-Ic28.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl and R¹⁵ is n-butylsulfonyl:

the compounds Ic29.01-Ic29.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is trifluoromethylsulfonyl:

the compounds Ic30.01-Ic30.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl and R¹⁵ is trifluoromethylsulfonyl:

the compounds Ic31.01-Ic31.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is phenylsulfonyl:

the compounds Ic32.01-Ic32.44, which differ from the corresponding compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl and R¹⁵ is phenylsulfonyl:

the compounds Ic33.01-Ic33.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is 4-methylphenylsulfonyl:

the compounds Ic34.01-Ic34.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl and R¹⁵ is 4-methylphenylsulfonyl:

the compounds Ic35.01-Ic35.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁶ is methyl:

the compounds Ic36.01-Ic36.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl and R¹⁶ is methyl:

the compounds Ic37.01-Ic37.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ and R¹⁶ are each methyl:

the compounds Ic38.01-Ic38.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl, and R¹⁵ and R¹⁶ are each methyl:

the compounds Ic39.01-Ic39.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is ethyl and R¹⁶ is methyl:

the compounds Ic40.01-Ic40.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ and R¹⁵ are each ethyl and R¹⁶ is methyl:

the compounds Ic40.01-Ic40.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is n-propyl and R¹⁶ is methyl:

the compounds Ic42.01-Ic42.22, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl, R¹⁵ is n-propyl and R¹⁶ is methyl:

the compounds Ic43.01-Ic43.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is n-butyl and R¹⁶ is methyl:

the compounds Ic44.01-Ic44.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl, R¹⁵ is n-butyl and R¹⁶ is methyl:

the compounds Ic45.01-Ic45.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is methylcarbonyl and R¹⁶ is methyl:

the compounds Ic46.01-Ic46.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl, R¹⁵ is methylcarbonyl and R¹⁶ is methyl:

the compounds Ic47.01-Ic47.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is ethylcarbonyl and R¹⁶ is methyl:

the compounds Ic48.01-Ic48.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl, R¹⁵ is ethylcarbonyl and R¹⁶ is methyl:

the compounds Ic49.01-Ic49.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is n-propylcarbonyl and R¹⁶ is methyl:

the compounds Ic50.01-Ic50.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl, R¹⁵ is n-propylcarbonyl and R¹⁶ is methyl:

the compounds Ic51.01-Ic51.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is n-butylcarbonyl and R¹⁶ is methyl:

the compounds Ic52.01-Ic52.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl, R¹⁵ is n-butylcarbonyl and R¹⁶ is methyl:

the compounds Ic53.01-Ic53.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is trifluoromethylcarbonyl and R¹⁶ is methyl:

the compounds Ic54.01-Ic54.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl, R¹⁵ is trifluoromethylcarbonyl and R¹⁶ is methyl:

the compounds Ic55.01-Ic55.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is methylsulfonyl and R¹⁶ is methyl:

the compounds Ic.56.01-Ic56.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl, R¹⁵ is methylsulfonyl and R¹⁶ is methyl:

the compounds Ic57.01-Ic57.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is ethylsulfonyl and R¹⁶ is methyl:

the compounds Ic58.01-Ic58.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl, R¹⁵ is ethylsulfonyl and R¹⁶ is methyl:

the compounds Ic59.01-Ic59.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is n-propylsulfonyl and R¹⁶ is methyl:

the compounds Ic60.01-Ic60.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl, R¹⁵ is n-propylsulfonyl and R¹⁶ is methyl:

the compounds Ic61.01-Ic61.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is n-butylsulfonyl and R¹⁶ is methyl:

the compounds Ic62.01-Ic62.044, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl, R¹⁵ is n-butylsulfonyl and R¹⁶ is methyl:

the compounds Ic63.01-Ic63.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is trifluoromethylsulfonyl and R¹⁶ is methyl:

the compounds Ic64.01-Ic64.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl, R¹⁵ is trifluoromethylsulfonyl and R¹⁶ is methyl:

the compounds Ic65.01-Ic65.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is phenylsulfonyl and R¹⁶ is methyl:

the compounds Ic66.01-Ic66.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl, R¹⁵ is phenylsulfonyl and R¹⁶ is methyl:

the compounds Ic67.01-Ic67.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁵ is 4-methylphenylsulfonyl and R¹⁶ is methyl:

the compounds Ic68.01-Ic68.44, which differ from the compounds Ic1.01-Ic1.44 in that R¹⁴ is ethyl, R¹⁵ is 4-methylphenylsulfonyl and R¹⁶ is methyl:

In addition, very particular preference is given to the compounds Id1 ({circumflex over (=)} I where R², R¹⁵, R¹⁶=H and R¹⁴=CH₃ and where the “Q-CO-fragment” is attached in position a, R¹ is attached in position d and Z² is attached in positions b and c) listed in Table 4 below:

TABLE 4 No. R¹ R³ R⁷ R⁹ Id1.01 Br H H H Id1.02 Cl H H H Id1.03 SO₂CH₃ H H H Id1.04 CH₃ H H H Id1.05 OH H H H Id1.06 OCH₃ H H H Id1.07 CF₃ H H H Id1.08 NO₂ H H H Id1.09 F H H H Id1.10 OCF₃ H H H Id1.11 Br CH₃ H H Id1.12 Cl CH₃ H H Id1.13 SO₂CH₃ CH₃ H H Id1.14 CH₃ CH₃ H H Id1.15 OH CH₃ H H Id1.16 OCH₃ CH₃ H H Id1.17 CF₃ CH₃ H H Id1.18 NO₂ CH₃ H H Id1.19 F CH₃ H H Id1.20 H CH₃ H H Id1.21 OCF₃ CH₃ H H Id1.22 Br CH₃ CH₃ H Id1.23 Cl CH₃ CH₃ H Id1.24 SO₂CH₃ CH₃ CH₃ H Id1.25 CH₃ CH₃ CH₃ H Id1.26 OH CH₃ CH₃ H Id1.27 OCH₃ CH₃ CH₃ H Id1.28 CF₃ CH₃ CH₃ H Id1.29 NO₂ CH₃ CH₃ H Id1.30 F CH₃ CH₃ H Id1.31 OCF₃ CH₃ CH₃ H Id1.32 Br Cl Cl Cl Id1.33 Cl Cl Cl Cl Id1.34 SO₂CH₃ Cl Cl Cl Id1.35 CH₃ Cl Cl Cl Id1.36 OH Cl Cl Cl Id1.37 OCH₃ Cl Cl Cl Id1.38 CF₃ Cl Cl Cl Id1.39 NO₂ Cl Cl Cl Id1.40 F Cl Cl Cl Id1.41 OCF₃ Cl Cl Cl Id1.42 Br OCH₃ Cl H Id1.43 Cl OCH₃ Cl H Id1.44 SO₂CH₃ OCH₃ Cl H Id1.45 CH₃ OCH₃ Cl H Id1.46 OH OCH₃ Cl H Id1.47 OCH₃ OCH₃ Cl H Id1.48 CF₃ OCH₃ Cl H Id1.49 NO₂ OCH₃ Cl H Id1.50 F OCH₃ Cl H Id1.51 OCF₃ OCH₃ Cl H Id1.52 Br H OCH₃ H Id1.53 Cl H OCH₃ H Id1.54 SO₂CH₃ H OCH₃ H Id1.55 CH₃ H OCH₃ H Id1.56 OH H OCH₃ H Id1.57 OCH₃ H OCH₃ H Id1.58 CF₃ H OCH₃ H Id1.59 NO₂ H OCH₃ H Id1.60 F H OCH₃ H Id1.61 OCF₃ H OCH₃ H Id1.62 Br CH₃ CH₃ CH₃ Id1.63 Cl CH₃ CH₃ CH₃ Id1.64 SO₂CH₃ CH₃ CH₃ CH₃ Id1.65 CH₃ CH₃ CH₃ CH₃ Id1.66 OH CH₃ CH₃ CH₃ Id1.67 OCH₃ CH₃ CH₃ CH₃ Id1.68 CF₃ CH₃ CH₃ CH₃ Id1.69 NO₂ CH₃ CH₃ CH₃ Id1.70 F CH₃ CH₃ CH₃ Id1.71 OCF₃ CH₃ CH₃ CH₃ Id1.72 Br Cl H H Id1.73 Cl Cl H H Id1.74 SO₂CH₃ Cl H H Id1.75 CH₃ Cl H H Id1.76 OH Cl H H Id1.77 OCH₃ Cl H H Id1.78 CF₃ Cl H H Id1.79 NO₂ Cl H H Id1.80 F Cl H H Id1.81 OCF₃ Cl H H Id1.82 Br Cl Cl H Id1.83 Cl Cl Cl H Id1.84 SO₂CH₃ Cl Cl H Id1.85 CH₃ Cl Cl H Id1.86 OH Cl Cl H Id1.87 OCH₃ Cl Cl H Id1.88 CF₃ Cl Cl H Id1.89 NO₂ Cl Cl H Id1.90 F Cl Cl H Id1.91 OCF₃ Cl Cl H

Furthermore, very particular preference is given to the following hetaroyl derivatives of the formula I:

the compounds Id2.01-Id2.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl:

the compounds Id.3.01-Id3.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is methyl:

the compounds Id4.01-Id4.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl and R¹⁵ is methyl:

the compounds Id5.01-Id5.91, which differ from the corresponding compounds Id1.01-Id1.91 in that R¹⁵ is ethyl:

the compounds Id6.01-Id6.91, which differ from the corresponding compounds Id1.01-Id1.91 in that R¹⁴ and R¹⁵ are each ethyl:

the compounds Id7.01-Id7.91, which differ from the corresponding compounds Id1.01-Id1.91 in that R¹⁵ is n-propyl:

the compounds Id8.01-Id8.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl and R¹⁵ is n-propyl:

the compounds Id9.01-Id9.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is n-butyl:

the compounds Id10.01-Id10.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl and R¹⁵ is n-butyl:

the compounds Id11.01-Id11.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is methylcarbonyl:

the compounds Id12.01-Id12.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl and R¹⁵ is methylcarbonyl:

the compounds Id13.01-Id13.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is ethylcarbonyl:

the compounds Id14.01-Id14.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl and R¹⁵ is ethylcarbonyl:

the compounds Id15.01-Id15.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is n-propylcarbonyl:

the compounds Id16.01-Id16.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl and R¹⁵ is n-propylcarbonyl:

the compounds Id17.01-Id17.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is n-butylcarbonyl:

the compounds Id18.01-Id18.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl and R¹⁵ is n-butylcarbonyl:

the compounds Id19.01-Id19.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is trifluoromethylcarbonyl:

the compounds Id20.01-Id20.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl and R¹⁵ is trifluoromethylcarbonyl:

the compounds Id21.01-Id21.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is methylsulfonyl:

the compounds Id22.01-Id22.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl and R¹⁵ is methylsulfonyl:

the compounds Id23.01-Id23.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is ethylsulfonyl:

the compounds Id24.01-Id24.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl and R¹⁵ is ethylsulfonyl:

the compounds Id25.01-Id25.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is n-propylsulfonyl:

the compounds Id26.01-Id26.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl and R¹⁵ is n-propylsulfonyl:

the compounds Id27.01-Id27.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is n-butylsulfonyl:

the compounds Id28.01-Id28.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl and R¹⁵ is n-butylsulfonyl:

the compounds Id29.01.-Id29.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is trifluoromethylsulfonyl:

the compounds Id30.01-Id30.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl and R¹⁵ is trifluoromethylsulfonyl:

the compounds Id31.01-Id31.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is phenylsulfonyl:

the compounds Id32.01-Id32.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl and R¹⁵ is phenylsulfonyl:

the compounds Id33.01-Id33.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is 4-methylphenylsulfonyl:

the compounds Id34.01-Id34.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl and R¹⁵ is 4-methylphenylsulfonyl:

the compounds Id35.01-Id35.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁶ is methyl:

the compounds Id36.01-Id36.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl and R¹⁶ is methyl:

the compounds Id37.01-Id37.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ and R¹⁶ are each methyl:

the compounds Id38.01-Id38.91, which differ from the compounds Id1.01-Id1.91 [sic] in that R¹⁴ is ethyl, and R¹⁵ and R¹⁶ are each methyl:

the compounds Id39.01-Id39.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is ethyl and R¹⁶ is methyl:

the compounds Id40.01-Id40.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ and R¹⁵ are each ethyl and R¹⁶ is methyl:

the compounds Id41.01-Id41.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is n-propyl and R¹⁶ is methyl:

the compounds Id42.01-Id41.92, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl, R¹⁵ is n-propyl and R¹⁶ is methyl:

the compounds Id43.01-Id43.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is n-butyl and R¹⁶ is methyl:

the compounds Id44.01-Id44.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl, R¹⁵ is n-butyl and R¹⁶ is methyl:

the compounds Id45.01-Id45.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is methylcarbonyl and R¹⁶ is methyl:

the compounds Id46.01-Id46.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl, R¹⁵ is methylcarbonyl and R¹⁶ is methyl:

the compounds Id47.01-Id47.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is ethylcarbonyl and R¹⁶ is methyl:

the compounds Id48.01-Id48.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl, R¹⁵ is ethylcarbonyl and R¹⁶ is methyl:

the compounds Id49.01-Id49.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is n-propylcarbonyl and R¹⁶ is methyl:

the compounds Id50.01-Id50.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl, R¹⁵ is n-propylcarbonyl and R¹⁶ is methyl:

the compounds Id51.01-Id51.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is n-butylcarbonyl and R¹⁶ is methyl:

the compounds Id52.01-Id52.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl, R¹⁵ is n-butylcarbonyl and R¹⁶ is methyl:

the compounds Id53.01-Id53.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is trifluoromethylcarbonyl and R¹⁶ is methyl:

the compounds Id54.01-Id54.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl, R¹⁵ is trifluoromethylcarbonyl and R¹⁶ is methyl:

the compounds Id55.01-Id55.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is methylsulfonyl and R¹⁶ is methyl:

the compounds Id56.01-Id56.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl, R¹⁵ is methylsulfonyl and R¹⁶ is methyl:

the compounds Id57.01-Id57.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is ethylsulfonyl and R¹⁶ is methyl:

the compounds Id58.01-Id58.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl, R¹⁵ is ethylsulfonyl and R¹⁶ is methyl:

the compounds Id59.01-Id59.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is n-propylsulfonyl and R¹⁶ is methyl:

the compounds Id60.01-Id60.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl, R¹⁵ is n-propylsulfonyl and R¹⁶ is methyl:

the compounds Id61.01-Id61.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is n-butylsulfonyl and R¹⁶ is methyl:

the compounds Id62.01-Id62.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl, R¹⁵ is n-butylsulfonyl and R¹⁶ is methyl:

the compounds Id63.01-Id63.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is trifluoromethylsulfonyl and R¹⁶ is methyl:

the compounds Id64.01-Id64.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl, R¹⁵ is trifluoromethylsulfonyl and R¹⁶ is methyl:

the compounds Id65.01-Id65.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is phenylsulfonyl and R¹⁶ is methyl:

the compounds Id66.01-Id66.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl, R¹⁵ is phenylsulfonyl and R¹⁶ is methyl:

the compounds Id67.01-Id67.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁵ is 4-methylphenylsulfonyl and R¹⁶ is methyl:

the compounds Id68.01-Id68.91, which differ from the compounds Id1.01-Id1.91 in that R¹⁴ is ethyl, R¹⁵ is 4-methylphenylsulfonyl and R¹⁶ is methyl:

The hetaroyl derivatives of the formula I can be obtained by different routes, for example by the following process:

Process A:

Reaction of hydroxypyrazoles of the formula II where R¹⁵=H with an activated carboxylic acid IIIa or a carboxylic acid IIIb which is preferably activated in situ to give the acylation product, and subsequent rearrangement.

L¹ represents a nucleophilically replaceable leaving group, such as halogen, for example bromine or chlorine, heterocyclyl, for example imidazolyl or pyridyl, or carboxylate, for example acetate, trifluoroacetate, etc.

The activated hetaroylcarboxylic acid can be employed directly, as in the case of the hetaroyl halides, or formed in situ, for example by using dicyclohexylcarbodiimide, triphenylphosphine/azodicarboxylic ester, 2-pyridine disulfite/triphenylphosphine, carbonyldiimidazole, etc.

It may be advantageous to carry out the acylation reaction in the presence of a base. It is advantageous to employ the reactants and the auxiliary base in equimolar amounts. In certain cases, a small excess of the auxiliary base, for example 1.2 to 1.5 molar equivalents based on II, may be advantageous.

Suitable auxiliary bases include tertiary alkylamines, pyridine and alkali metal carbonates. Suitable solvents are, for example, chlorinated hydrocarbons, such as methylene chloride and 1,2-dichloroethane, aromatic hydrocarbons, such as toluene, xylene and chlorobenzene, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran and dioxane, polar aprotic solvents, such as acetonitrile, dimethylformamide or dimethyl sulfoxides or esters, such as ethyl acetate, or mixtures thereof.

If carboxylic acid halides are employed as activated carboxylic acid component, it may be advantageous to cool the reaction mixture to 0-10°0 C. when adding this reactant. Stirring is then continued at 20-100° C., preferably at 25-50° C., until the reaction has ended. Work-up is carried out in a conventional manner; for instance, the reaction mixture is poured into water and the product of value is extracted. Suitable solvents for this purpose are in particular methylene chloride, diethyl ether and ethyl acetate. After drying of the organic phase and removal of the solvent, the crude ester can be used for the rearrangement without any further purification.

The rearrangement of the esters to give the compounds of the formula I is advantageously carried out at from 20 to 40° C. in a solvent and in the presence of an auxiliary base and optionally using a cyano compound as catalyst.

Suitable solvents are, for example, acetonitrile, methylene chloride, 1,2-dichloroethane, dioxane, ethyl acetate, toluene, or mixtures thereof. Preferred solvents are acetonitrile and dioxane.

Suitable auxiliary bases are tertiary amines, such as triethylamine, pyridine or alkali metal carbonates, such as sodium carbonate and potassium carbonate, which are preferably employed in equimolar amounts or up to a fourfold excess, based on the ester. Preference is given to using triethylamine or alkali metal carbonates, preferably in double the equimolar amount based on the ester.

Suitable “rearrangement catalysts” include inorganic cyanides, such as sodium cyanide and potassium cyanide, and organic cyano compounds, such as acetone cyanohydrin and trimethylsilyl cyanide. They are employed in an amount of from 1 to 50 mol percent, based on the ester. Preference is given to using acetone cyanohydrin or trimethylsilyl cyanide, for example in an amount of from 5 to 15, preferably 10, mol percent based on the ester.

Work-up can be carried out in a known manner. The reaction mixture is acidified, for example with dilute mineral acid, such as 5% strength hydrochloric acid or sulfuric acid, and extracted with an organic solvent, for example methylene chloride or ethyl acetate. The organic extract can be extracted with 5-10% strength alkali metal carbonate solution, for example with sodium carbonate solution or potassium carbonate solution. The aqueous phase is acidified and the resulting precipitate is filtered off with suction and/or extracted with methylene chloride or ethyl acetate, dried and concentrated.

(Examples of the preparation of esters of hydroxypyrazoles and of the rearrangement of the esters are described, for example, in EP-A 282 944 and U.S. Pat. No. 4,643,757).

Process B:

Reaction of hetaroyl derivatives of the formula I where R¹⁵=H with a compound of the formula IV (where R¹⁵≠H):

L² is a nucleophilically replaceable leaving group, such as halogen, for example bromine and chlorine, heterocyclyl, for example imidazolyl and pyridyl, carboxylate, for example acetate and trifluoroacetate, or sulfonate, for example mesylate and triflate, etc.

The compounds of the formula IV can be employed directly, for example in the case of alkyl halides, acyl halides, sulfonyl halides, carboxylic acid anhydrides and sulfonic acid anhydrides, or formed in situ, for example activated carboxylic acids (by using a carboxylic acid and dicyclohexylcarbodiimide, carbonyldiimidazole, etc.).

The starting materials are usually employed in an equimolar ratio. However, it may be advantageous to use an excess of one or other of the components.

It may be advantageous to carry out the reaction in the presence of a base. The reactants and the auxiliary base are advantageously employed in equimolar amounts. In some instances, an excess of the auxiliary base, for example 1.5 to 3 molar equivalents based on II, may be advantageous.

Suitable auxiliary bases are tertiary alkylamines, such as triethylamine or pyridine, alkali metal carbonates, for example sodium carbonate and potassium carbonate, and alkali metal hydrides, for example sodium hydride. Preference is given to triethylamine and pyridine.

Suitable solvents are, for example, chlorinated hydrocarbons, such as methylene chloride and 1,2-dichloroethane, aromatic hydrocarbons, for example toluene, xylene and chlorobenzene, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran and dioxane, polar aprotic solvents, such as acetonitrile, dimethylformamide and dimethyl sulfoxide, or esters, such as ethyl acetate, or mixtures thereof.

The reaction temperature is generally in the range of from 0° C. to the boiling point of the reaction mixture.

Work-up is carried out in a conventional manner to afford the product.

Those hydroxypyrazoles of the formula II (where R¹⁵=H) used as starting materials which are not already known can be obtained in a conventional manner (for example EP-A 240 001, J. Prakt. Chem. 315 (1973), 383).

The carboxylic acid halides of the formula IIIa (where L¹=Br, C1) which are not already known can be obtained in a conventional manner by reacting the carboxylic acids of the formula IIIb with halogenating reagents such as thionyl chloride, thionyl bromide, phosgene, diphosgene, triphosgene, oxalyl chloride and oxalyl bromide.

Those carboxylic acids of the formula IIIb which are not already known can be obtained in a conventional manner (The Chemistry of Heterocyclic Compounds, Vol. 32, “Quinolines, Part I, II and III”, Editor E. Taylor, publisher Wiley & Sons; The Chemistry of Heterocyclic Compounds, Vol. 38, “Isoquinolines, Part I and II”, Editor A. Weissemberger and E. Taylor, publisher Wiley & Sons; T. Eicher, S. Hauptmann, “Chemie der Heterocyclen”, Thieme Verlag 1994).

For example, unsubstituted or substituted aminobenzoic acids can be reacted with glycerol, unsubstituted or substituted glycerol derivatives or α,β-unsaturated carbonyl compounds by the method of Skraup to give the corresponding quinolinecarboxylic acids (cf. EP-A 294 685, DE-A 33 26 225) (Scheme 1)

Likewise, it is possible to react unsubstituted or substituted anilines with glycerol, unsubstituted or substituted glycerol derivatives or α,β-unsaturated carbonyl compounds. After halogenation and exchange of the halogen function by cyanide (for example using copper(I) cyanide), the nitrile is hydrolyzed to give the corresponding quinolinecarboxylic acid (cf. Khim. Greterotsikl. Soedin 3 (1980), 366 ({circumflex over (=)} CA 93, 71504)). (Scheme 2)

Anilines which are not already known from the literature can be obtained by reducing the corresponding nitrobenzenes. Suitable for this purpose is for example catalytic hydrogenation, using, for example, Raney nickel, Pt/C, Pd/C or Rh/C, or reduction with iron powder, zinc powder, etc. in a mixture of organic acid, for example acetic acid or propionic acid, and a protic solvent, such as methanol, ethanol or water.

The nitrobenzenes can be synthesized by nitration, substitution reactions, etc. Scheme 3 exemplifies a synthetic sequence.

Isoquinolinecarboxylic acids can be synthesized for example from halogenated isoquinolines by halogen/cyanide exchange (Chem. Ber. 52 (1919), 1749) and subsequent hydrolysis. (Scheme 4)

It is also possible to prepare the corresponding aminoisoquinolines from nitrated isoquinolines by reduction (as mentioned above). Subsequent diazotization, Sandmeyer reaction with cyanide and hydrolysis afford isoquinolinecarboxylic acids (Scheme 5).

Halogenated or nitrated isoquinolines can be prepared according to EP-A 633 262. Furthermore, it is possible to obtain halogenated isoquinolines starting from unsubstituted or substituted benzaldehydes by reaction with aminoacetaldehyde acetal and subsequent halogenation (Helv. Chim. Acta 68 (1985), 1828) (Scheme 6).

The N-oxides of the quinoline- or isoquinolinecarboxylic acids can be obtained from the corresponding quinoline- or isoquinolinecarboxylic acids by oxidation with hydrogen peroxide. It may be advantageous to convert the corresponding acids first into the C₁-C₆-alkyl esters, to carry out the oxidation with hydrogen peroxide and then hydrolyze the ester.

2,3-Dihydroquinoline derivatives can be obtained, inter alia, by cyclization of γ-functionalized N-alkylanilines, with or without using Lewis acids or protic acids (Heterocycles 24 (1986), 2109; J. Am. Chem. Soc. 71 (1949), 1901).

Tetrahydroisoquinoline derivatives can be obtained from isoquinolines by reduction with hydrogen, if appropriate by metal catalysis, for example by Pt in acetic acid. However, it is also possible to react isoquinolines with dimethyl sulfate and to convert them into tetrahydroisoquinoline derivatives by reduction with sodium borohydride.

The compounds of the formula IV which are not already known from the literature can be obtained by the methods of known processes.

Preparation Examples 4-[(8-Bromoquinolin-5-yl)carbonyl]-1-ethyl-5-hydroxypyrazole (compound 5.01)

1.00 g of 8-bromoquinoline-5-carboxylic acid, 0.44 g of 1-ethyl-5-hydroxypyrazole and 0.80 g of dicyclohexylcarbodiimide were stirred in 15 ml of acetonitrile at room temperature. After the addition of 0.2 ml of acetone cyanohydrin and 0.60 g of triethylamine, stirring was continued for 1.5 hours and the mixture was then poured into aqueous sodium carbonate solution. The alkaline phase was washed with ethyl acetate and diethyl ether and then acidified. The precipitate was filtered off under suction and the aqueous phase was extracted with ethyl acetate. This organic phase was dried and concentrated. The residue and the precipitate were combined.

Yield: 0.64 g

(Melting point: 125° C.)

5-Hydroxy-1-methyl-4-[(8-methylquinolin-5-yl)carbonyl]pyrazole (compound 5.04) Step 1: 8-methyl-5-quinolinecarbonyl chloride

10.00 g of 8-methylquinoline-5-carboxylic acid in 100 ml of toluene together with 7.00 g of thionyl chloride and 3 drops of dimethylformamide were heated under reflux for 2.5 hours. The solvent was distilled off and the acyl chloride obtained was used directly for further reactions.

Step 2: 5-hydroxy-l-methyl-4-[(8-methylquinolin-5-yl)carbonyl]-pyrazole

At 0° C., 1.70 g of 8-methylquinoline-5-carbonyl chloride were added to 0.81 g of 5-hydroxy-1-methylpyrazole and 0.92 g of triethylamine in 30 ml of acetonitrile. The reaction mixture was stirred for 3 hours at room temperature and then taken up in ethyl acetate and washed with aqueous sodium carbonate solution, and the organic phase was then dried and concentrated. The residue was treated with 10 ml of dioxane and 1.71 g of dry potassium carbonate and heated under reflux for 14 hours. After cooling, water was added and the aqueous phase was washed with ethyl acetate and acidified with 2N hydrochloric acid. The precipitate was filtered off under suction and the acidified aqueous phase was extracted with ethyl acetate. This organic phase was dried and concentrated. The residue and the precipitate were combined.

Yield: 0.97 g

(Melting point: 158-160° C.)

4-[(8-Chloroquinolin-5-yl)carbonyl]-5-(4-chlorophenylsulfonyloxy) -1-ethylpyrazole (compound 5.26)

1.00 g of 4-[(8-chloroquinolin-5-yl)carbonyl]-1-ethyl-5-hydroxy-pyrazole, 0.70 g of triethylamine and 0.70 g of 4-chlorobenzenesulfonyl chloride in 15 ml of methylene chloride were stirred at room temperature for 12 hours. The reaction mixture was then poured into aqueous sodium carbonate solution and extracted with ethyl acetate. The combined organic phases were dried and concentrated and the residue was purified by chromatograpy over silica gel.

Yield: 1.00 g

(Melting point: 98° C.)

In addition to the hetaroyl derivatives of the formula I described above, further hetaroyl derivatives of the formula I which have been or can be prepared in a similar manner are listed in Table 5 below:

TABLE 5 Ia (where R² = H)

physical data ¹H-NMR [ppm] No. R¹ R⁵ R⁷ R⁹ R¹⁴ R¹⁵ R¹⁶ mp [° C.] 5.01 Br H H H n-C₂H₅ H H 125 5.02 OCH₃ H H H C₂H₅ H H  58 5.03 CH₃ H H H C₂H₅ H H 104-106 5.04 CH₃ H H H CH₃ H H 158-160 5.05 OCH₃ H H H CH₃ H CH₃ 218 5.06 Br H H H CH₃ H H 176 5.07 OCH₃ H H H CH₃ H H 151 5.08 Br H H H CH₃ H CH₃  82 5.09 CH₃ H H H CH₃ H CH₃  57 5.10 Cl H H H CH₃ H CH₃  87 5.11 Cl H H H C₂H₅ H H 140-142 5.12 SO₂CH₃ H H H C₂H₅ H H 159-161 5.13 SO₂CH₃ H H H CH₃ H CH₃ 148-150 5.14 Cl H H H CH₃ H H 194-197 5.15 SO₂CH₃ H H H CH₃ H H 148-150 5.16 Cl CH₃ H H C₂H₅ H H 138-140 5.17 Cl CH₃ H H CH₃ H H 217-219 5.18 Cl CH₃ H H CH₃ H CH₃ 218 5.19 Cl H CH₃ H CH₃ H H 243 5.20 Cl H CH₃ H C₂H₅ H H 134 5.21 Cl H CH₃ H CH₃ H CH₃ 117-119 5.22 F H H H C₂H₅ H H 113 5.23 F H H H CH₃ H CH₃ 249-252 5.24 Cl H H H C₂H₅

H 132 5.25 Cl H H H C₂H₅ SO₂—(CH₂)₃CH₃ H  94 5.26 Cl H H H C₂H₅

H  98 5.27 SO₂CH₃ H H H i-C₄H₉ H H 184 5.28 SO₂CH₃ H CH₃ H n-C₃H₇ H H 176 5.29 SO₂CH₃ H CH₃ H CH₃ H H 140 5.30 SO₂CH₃ H CH₃ H CH₃ H CH₃ 1.63(s, 3H); 2.59(s, 3H); 3.66(s, 3H); 3.70(s, 3H); 7.64(d, 1H); 8.18(d, 1H); 8.56(d, 1H); 9.00(d, 1H); 5.31 SO₂CH₃ H CH₃ H n-C₄H₉ H H 159 5.32 SO₂CH₃ CH₃ H H CH₃ H CH₃  83 5.33 SO₂CH₃ CH₃ H H C₂H₅ H H 186 5.34 SO₂CH₃ CH₃ H H i-C₄H₉ H H 1.00(d, 6H); 2.29(m, 1H); 2.82(s, 3H); 3.65(s, 3H); 3.83(d, 2H); 5.18(bs, 1H); 7.48(s, 1H); 7.50(d, 1H); 7.91(d, 1H); 8.61(d, 1H); 8.63(d, 1H); 5.35 SO₂CH₃ CH₃ H H n-C₄H₉ H H  60 5.36 SO₂CH₃ CH₃ H H n-C₃H₇ H H  70 5.37 Cl CH₃ CH₃ H C₂H₅ H H 129 5.38 Cl H H H C₂H₅ CO-n-C₃H₇ H  85 5.39 Cl H H H C₂H₅

H 166 5.40 Br H H H C₂H₅ CO-n-C₃H₇ H  82 5.41 Br H H H C₂H₅

H 132 5.42 Cl H H H C₂H₅

H 106 5.43 Br H H H C₂H₅ CH₃ H 120 5.44 Cl H H H C₂H₅ CO—O-n-C₃H₇ H  85 5.45 Cl H H H C₂H₅ CO—CH₃ H 153 5.46 Br H H H C₂H₅ C₂H₅ H 123 5.47 Br H H H C₂H₅

H  79 5.48 Br H H H C₂H₅ CH₃ H 117 5.49 Br H H H C₂H₅

H 154 5.50 Cl H H H C₂H₅ C₂H₅ H 130 5.51 Cl H H H C₂H₅

H 148 5.52 Br H H H C₂H₅ CO—O-n-C₃H₇ H 1.00(t, 3H); 1.50(m, 3H); 1.78(m, 2H); 4.17(m, 4H); 7.52(m, 1H); 7.67(m, 2H); 8.15(m, 1H); 8.62(m, 1H); 9.08(m, 1H); 5.53 Br H H H C₂H₅

H 137 5.54 Br H H H C₂H₅ CO-CH₃ H 154

The syntheses of some carboxylic acids of the formula IIIb are listed below:

8-Methylsulfonyl-5-quinolinecarboxylic acid (Compound 6.06) Step 1: 3-Nitro-4-(methylthio)benzoic acid

0.75 mol of 4-fluoro-3-nitrobenzoic acid was charged in 2 l of methanol, and 0.75 mol of sodium methoxide was added dropwise. 0.83 mol of sodium thiomethoxide was then added and the reaction mixture was heated to 55-60° C. for 5 hours. After cooling, 1 l of water was added, the precipitate was filtered off with suction and washed with 100 ml of methylene chloride. The residue was then taken up in 500 ml of 2 N hydrochloric acid and the precipitate formed was filtered off with suction and washed with water. The residue was then taken up in tetrahydrofuran and dried over sodium sulfate and the solvent was distilled off.

Yield: 127.6 g (79%) (yellow solid)

(Melting point: 245-247° C.)

Step 2: 3-Nitro-4-methylsulfonylbenzoic acid

0.22 mol of 3-nitro-4-(methylthio)benzoic acid was charged together with 800 ml of glacial acetic acid and 5.4 g of Na₂WO₄·2 H₂O. At a temperature of 55° C., 1.32 mol of H₂O₂ (30% strength) were added dropwise. The mixture was then stirred for 20 minutes at 50° C. and for 2 hours at 70° C. After cooling, the reaction solution was stirred into 1 l of water, the precipitate was filtered off with suction, the residue was washed with water and the product was dried under reduced pressure.

Yield: 47.4 g (88%) (white crystals)

(IR (υ in cm⁻¹): 1699, 1558, 1371, 1322, 1155)

Step 3: 3-Amino-4-methylsulfonylbenzoic acid

0.447 mol of 3-nitro-4-methylsulfonylbenzoic acid was reduced with hydrogen by employing 100 g of Raney nickel in 2.5 l of methanol. The mixture was then heated to reflux and filtered off hot with suction. The filtrate was concentrated.

Yield: 88.1 g (91%)

(¹H—NMR (d₆-DMSO, δ in ppm): 3.18 (3H); 6.25 (2H); 7.21 (1H); 7.48 (1H); 7.72 (1H); 13.8 (1H))

Step 4: 8-Methylsulfonyl-5-quinolinecarboxylic acid

38 ml of water and 102 g of concentrated sulfuric acid were heated to 110° C. At 95° C., 0.25 mol of 3-amino-4-methylsulfonylbenzoic acid was added. The mixture was then heated to 140° C., and 0.8 g of sodium iodide and 0.3 mol of glycerol were added. The reaction temperature was then increased to 150° C. While the mixture was heated to and stirred at 150° C. (1 hour), 47 g of distillate were collected. After cooling, the reaction mixture was carefully admixed with 200 ml of water and diluted with a further 800 ml of water. Using 20% strength aqueous sodium hydroxide solution, the pH was adjusted to 13 and the mixture was filtered and adjusted to pH 3.5 with sulfuric acid. This procedure was repeated. A precipitate was formed which was filtered off with suction. The filtrate was adjusted to pH=2 and the resulting precipitate was filtered off with suction, washed with water and dried.

Yield: 44.9 g (71%)

(¹H—NMR (d₆-DMSO, δin ppm): 3.70 (3H); 7.82 (1H); 8.40 (1B); 8.68 (1H); 9.32 (1H); 9.66 (1H), 14.01 (1H))

8-Bromoquinoline-5-carboxylic acid (Compound 6.05) Step 1: 5-Amino-8-bromoquinoline

At reflux, 10.0 g of 8-bromo-5-nitroquinoline in 68 ml of glacial acetic acid and 34 ml of ethanol were added dropwise to a mixture of 7.75 g of iron powder, 18 ml of glacial acetic acid and 9 ml of ethanol. After stirring for 45 minutes at reflux, the mixture was cooled and filtered through diatomaceous earth. The filtrate was concentrated, taken up in methylene chloride, washed with sodium carbonate solution, dried and concentrated.

Yield: 7.90 g

(¹H—NMR (CDCl₃; δ in ppm): 4.22 (bs, 2H); 7.71 (m,1H); 7.40 (m,1H); 7.80 (m,1H); 8.18 (m,1H); 9.00 (m,1H))

Step 2: 8-Bromo-5-cyanoquinoline

0.60 g of concentrated hydrochloric acid was added dropwise to a mixture of 0.70 g of 5-amino-8-bromoquinoline and 3.15 ml of acetic acid, and the mixture was stirred for 1 hour at room temperature. At 0-50° C., 0.22 g of sodium nitrite in 0.45 ml of water were then added, and the mixture was stirred for 1 hour. After the addition of 20 mg of urea in 0.16 ml of water, stirring was continued at 0-50° C. for a further hour. This solution is added to a two-phase system of toluene/copper(I) cyanide solution which was prepared as follows: a solution of 0.79 g of copper(II) sulfate in 2.2 ml of water was added dropwise to a solution of 1.06 g of 10% strength ammonia solution and 0.77 g of sodium cyanide, and 6 ml of toluene were added to this mixture to form a lower layer. After stirring for 1 hour at room temperature, insoluble particles were filtered off and the solution was extracted with ethyl acetate. The organic phase was dried and the solvent was removed under reduced pressure.

Yield: 0.50 g

(¹H—NMR (CDCl₃; δ in ppm): 7.61 (m,1H); 7.76 (m,1H); 8.19 (m,1H); 8.59 (m,1H); 9.17 (m,1H))

Step 3: 8-Bromoquinoline-5-carboxylic acid

At 150° C., 5.0 g of 8-bromo-5-cyanoquinoline were added a little at a time to 10.10 g of 75% strength sulfuric acid. After one hour, the reaction mixture was cooled, poured into ice water and extracted with ethyl acetate. The organic phase was dried and concentrated.

Yield: 3.6 g

(¹H—NMR (d₆-DMSO; δ a in ppm): 7.80 (m,1H); 8.18 (m,1H); 8.30 (m,1H); 9.15 (m,1H); 9.40 (m,1H))

5-Nitroquinoline-6-carboxylic acid (Compound 7.01) Step 1: 5-Nitro-6-methylquinoline

2.45 mol of 6-methylquinoline were added to 1 l of concentrated sulfuric acid, and 2.94 mol of 65% strength nitric acid were added dropwise at 0 to 10° C. The mixture was stirred for 1 hour, poured onto ice, adjusted to pH 2.5 with aqueous sodium hydroxide solution, filtered off with suction, washed with water and dried over magnesium sulfate.

Yield: 313.0 g of colorless crystals

(¹H—NMR (CDCl₃; δ in ppm): 2.55 (s,3H); 7.55 (q,1H); 7.60 (d,1H); 8.10 (d,1H); 8.15 (d,1H); 8.95 (q,1H))

Step 2: 5-Nitroquinoline-6-carboxylic acid

20.0 g of vanadium pentoxide and 0.74 mol of 5-nitro-6-methylquinoline were added to 1.3 1 of sulfuric acid, and 200 ml of 65% strength nitric acid are metered in at 140° C. over a period of 40 hours using a metering pump. The solution was subsequently poured onto ice, adjusted to pH 8.0 using aqueous sodium hydroxide solution, filtered off with suction and dried over magnesium sulfate. 81.0 g of starting material was recovered. The mother liquor was adjusted to pH 2.5 with sulfuric acid, filtered off with suction and dried over magnesium sulfate.

Yield: 67.0 g of colorless crystals

(¹H—NMR (d₆-DMSO; δ in ppm): 7.80 (q,1H); 8.20 (d,1H); 8.25 (d,1H); 8.40 (d,1H); 9.20 (d,1H))

5-Nitroquinoline-8-carboxylic acid (Compound 9.03) Step 1: 8-Cyano-5-nitroquinoline

5.80 g of 8-bromo-5-nitroquinoline and 2.00 g of copper(I) cyanide in 15 ml of dimethylformamide were heated to 150° C. for 5 hours. After cooling, methylene chloride was added, insoluble particles were filtered off and the filtrate was concentrated.

Yield: 3.90 g

(¹H—NMR (CDCl₃; δ in ppm): 7.84 (m,1H); 8.37 (m,1H); 8.40 (m,1H); 9.00 (m,1H); 9.24 (m,1H))

Step 2: 5-Nitroquinoline-8-carboxylic acid

At 150° C., 1.50 g of 8-cyano-5-nitroquinoline were added a little at a time to 3.50 g of 75% strength sulfuric acid. After stirring for one hour, the reaction mixture was cooled, poured into ice water and extracted with ethyl acetate. The organic phase was dried and the solvent was removed under reduced pressure.

Yield: 1.1 g (Melting point: 210° C.)

(¹H—NMR (d₆-DMSO; δ in ppm): 8.00 (m,1H); 8.49 (m,1H); 8.58 (m,1H); 9.01 (m,1H); 9.22 (m,1H); 15.0 (bs,1H))

1-Acetyl-2,3-dihydro-4-quinolone-7-carboxylic acid (Compound 11.02) Step 1: N-(2-Cyanoethyl)-3-aminobenzoic acid

200.0 g of 3-aminobenzoic acid in 2 l of water were admixed with 53.2 g of sodium hydroxide. At 30° C., 126.6 g of acrylonitrile were added dropwise, and the mixture was then heated under reflux for 22 hours. The mixture was then cooled to 5° C. and acetic acid was added (pH=5) and the precipitate which had formed was filtered off with suction and washed with water.

Yield: 266.3 g

(¹H—NMR (d₆-DMSO; δ in ppm): 2.75 (2H); 3.38 (2H); 6.21 (1H); 6.87 (1H); 7.21 (2H); 12.70 (1H))

Step 2: N-(2-Carboxyethyl)-3-aminobenzoic acid

266.0 g of N-(2-cyanoethyl)-3-aminobenzoic acid together with 336.0 g of sodium hydroxide in 3 l of water were heated under reflux for 5 hours. After cooling, the pH was adjusted to 3 with hydrochloric acid, the mixture was cooled and the precipitate was filtered off with suction.

Yield: 269.2 g

(Melting point: 211° C.)

Step 3: 2,3-Dihydro-4-quinolone-7-carboxylic acid

At 110° C., 50.0 g of the carboxylic acid of Step 2 were added a little at a time to 500.0 g of polyphosphoric acid. Stirring was continued for 1 hour. The reaction mixture was then poured onto ice, the precipitate was separated off and the mixture was extracted with ethyl acetate. The organic phase was then dried and concentrated.

Yield: 9.2 g

(¹H—NMR (d₆-DMSO; δ in ppm): 2.52 (2H); 3.41 (2H); 7.05 (2H); 7.40 (1H); 7.65 (1H))

Step 4: 1-Acetyl-2,3-dihydro-4-quinolone-7-carboxylic acid

5.0 g of 2,3-dihydro-4-quinolone-7-carboxylic acid and 22.5 g of acetic anhydride were heated to 100° C. for 1 hour. After cooling, water was added and the mixture was extracted with methylene chloride. The organic phase was dried and concentrated.

Yield: 4.8 g

(Melting point: 150° C.)

1, 8-Dimethyl-1,2,3,4-tetrahydroquinoline-5-carboxylic acid (Compound 13.01) Step 1: 8-Methyl-1,2,3,4-tetrahydroquinoline-5-carboxylic acid

0.1 mol of 8-methylquinoline-5-carboxylic acid was suspended in 1.5 l of ethanol and admixed with 10.0 g of palladium on activated carbon (5%). Over a period of 48 hours, the mixture was reduced in an autoclave at 50° C. using hydrogen (1 bar) (HPLC control). The reaction mixture was then filtered, the filter cake was washed with ethanol and the combined organic filtrates were concentrated.

Yield: 17.4 g of a yellow solid

(¹H—NMR (d₆-DMSO; δ in ppm): 1.75 (m,2H); 2.05 (s,3H); 2.90 (m,2H); 3.25 (m,2H); 5.10 (brs,2H); 6.80 (d,1H); 6.90 (d,1H))

(Melting point: 130° C.)

Step 2: 1,8-Dimethyl-1,2,3,4-tetrahydroquinoline-5-carboxylic acid

24 mmol of sodium cyanoborohydride were added to 5 mmol of 8-methyl-1,2,3,4-tetrahydroquinoline-5-carboxylic acid and 50 mmol of paraformaldehyde in 30 ml of glacial acetic acid, the temperature being kept below 30° C. using an ice bath. The mixture was stirred at room temperature for 15 hours and then poured onto ice and adjusted to pH 4 using aqueous sodium hydroxide solution. The mixture was then extracted with ethyl acetate and the organic phase was washed with water, dried over sodium sulfate and concentrated.

Yield: 0.75 g of colorless crystals

(¹H—NMR (d₆-DMSO; δ in ppm): 1.75 (m,2H); 2.25 (s,3H); 2.65 (s,3H); 3.00 (m,4H); 7.05 (d,1H); 7.30 (d,1H)

In addition to the carboxylic acids of the formula IIIb described above, further carboxylic acids of the formula IIIb which were or can be prepared in a similar manner are listed in Tables 6-12 below:

TABLE 6 IIIb

physical data No. R¹ R⁵ R⁷ R⁹ ¹H-NMR [ppm]; mp [° C.] 6.01 F H H H 7.66(m, 1H); 7.80(m, 1H); 8.30 (m, 1H); 9.01(m, 1H); 9.55 (m, 1H); 6.02 Cl H H H 7.80(m, 1H); 8.09(m, 1H); 8.25 (m, 1H); 9.10(m, 1H); 9.41(m, 1H); 13.1(bs, 1H); 6.03 Cl H CH₃ H 2.56(s, 3H); 7.91(m, 1H); 8.15 (m, 1H); 8.96(m, 1H); 9.16(m, 1H); 13.1(bs, 1H); 6.04 Cl CH₃ H H 2,73(s, 3H); 7.49(m, 1H); 7.65 (m, 1H); 8.14(m, 1H); 9.23(m, 1H); 13.1(bs, 1H); 6.05 Br H H H 7.80(m, 1H); 8.18(m, 1H); 8.30 (m, 1H); 9.15(m, 1H); 9.40(m, 1H); 6.06 SO₂CH₃ H H H 3.70(s, 3H); 7.82(m, 1H); 8.40 (m, 1H); 8.68(m, 1H); 9.32(m, 1H); 9.66(m, 1H); 14.01(bs, 1H); 6.07 SO₂CH₃ H CH₃ H 2.60(s, 3H); 3.63(s, 3H); 8.26 (m, 1H); 8.40(m, 1H); 9.10(m, 1H); 9.14(m, 1H); 6.08 SO₂CH₃ CH₃ H H 2.80(m, 3H); 3.66(s, 3H); 7.70 (m, 1H); 8.28(m, 1H); 8.45(m, 1H); 9.16(m, 1H); 6.09 CH₃ H H H 290 6.10 OH H H H 7.39(m, 1H); 7.90(m, 1H); 8.33 (m, 1H); 8.89(m, 1H); 9.70 (m, 1H); 6.11 OCH₃ H H H 4.04(s, 3H); 7.33(m, 1H); 7.68 (m, 1H); 8.31(m, 1H); 8.90(m, 1H); 9.60(m, 1H);

TABLE 7 IIIb

physical data No. R¹ R⁵ R⁷ R⁹ ¹H-NMR [ppm] 7.01 NO₂ H H H 7.80(q, 1H); 8.20(d, 1H); 8.25(d, 1H); 8.40(d, 1H); 9.20(d, 1H) 7.02 Cl H H H 7.03 Br H H H

TABLE 7 IIIb

physical data No. R¹ R⁵ R⁷ R⁹ ¹H-NMR [ppm] 7.01 NO₂ H H H 7.80(q, 1H); 8.20(d, 1H); 8.25(d, 1H); 8.40(d, 1H); 9.20(d, 1H) 7.02 Cl H H H 7.03 Br H H H

TABLE 9 IIIb

physical data No. R¹ R⁵ R⁷ R⁹ mp [° C.] 9.01 Cl H H H 199 9.02 SO₂CH₃ H H H 231 9.03 NO₂ H H H 210 9.04 H H H H 177

TABLE 9 IIIb

physical data No. R¹ R⁵ R⁷ R⁹ mp [° C.] 9.01 Cl H H H 199 9.02 SO₂CH₃ H H H 231 9.03 NO₂ H H H 210 9.04 H H H H 177

TABLE 9 IIIb

physical data No. R¹ R⁵ R⁷ R⁹ mp [° C.] 9.01 Cl H H H 199 9.02 SO₂CH₃ H H H 231 9.03 NO₂ H H H 210 9.04 H H H H 177

TABLE 12 IIIb

physical data No. R¹ R¹¹ ¹H-NMR [ppm] 12.01 H COCH₃ 2.36(s, 3H); 2.85(m, 2H); 4.17(m, 2H); 7.89(m, 1H); 8.09(m, 1H); 8.40(m, 1H); 13.1(bs, 1H);

TABLE 12 IIIb

physical data No. R¹ R¹¹ ¹H-NMR [ppm] 12.01 H COCH₃ 2.36(s, 3H); 2.85(m, 2H); 4.17(m, 2H); 7.89(m, 1H); 8.09(m, 1H); 8.40(m, 1H); 13.1(bs, 1H);

The compounds of the formula I and their agriculturally useful salts are suitable as herbicides, both in the form of isomer mixtures and in the form of the pure isomers. The herbicidal compositions comprising compounds of the formula I are capable of controlling vegetation on non-crop areas very efficiently, especially at high application rates. In crops such as wheat, rice, maize, soya and cotton, they act against broad-leaved weeds and grass weeds without causing any significant damage to the crop plants. This effect is observed mainly at low application rates.

Depending on the application method employed, the compounds of the formula I, or the herbicidal compositions comprising them, can additionally be employed in a further number of crop plants for eliminating undesirable plants. Examples of suitable crops are the following:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.

In addition, the compounds of the formula I can also be used in crops which tolerate the action of herbicides owing to breeding including genetic engineering methods.

The compounds of the formula I, or the herbicidal compositions comprising them, can be used for example in the form of directly sprayable aqueous solutions, powders, suspensions, also highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules by means of spraying, atomizing, dusting, spreading or watering. The use forms depend on the intended purposes; in any case, they should ensure the finest possible distribution of the active ingredients according to the invention.

Suitable inert auxiliaries are essentially: mineral oil fractions of medium to high boiling point, such as kerosine or diesel oil, further coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. paraffins, tetrahydronaphthalene, alkylated naphthalenes or their derivatives and alkylated benzenes or their derivatives, alcohols, such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones, such as cyclohexanone, or strongly polar solvents, eg. amines, such as N-methylpyrrolidone, or water.

Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substrates [sic], as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetting agent, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetting agent, tackifier, dispersant or emulsifier and, if desired, solvent or oil, these concentrates being suitable for dilution with water.

Suitable surfactants (adjuvants) are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, eg. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, of alkyl- and alkylarylsulfonates, of alkyl, lauryl ether and fatty alcohol sulfates, and the salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ether, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene, or of naphthalenesulfonic acids, with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.

Powders, materials for spreading and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Granules, eg. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, or other solid carriers.

The concentrations of the active ingredients of the formula I in the ready-to-use preparations can be varied within wide ranges. In general, the formulations comprise, for instance, from 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

The following Formulation Examples illustrate the preparation of such formulations:

I. 20 parts by weight of the compound No. 5.01 are dissolved in a mixture composed of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonate and 5 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

II. 20 parts by weight of the compound No. 5.04 are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

III. 20 parts by weight of the active ingredient No. 5.11 are dissolved in a mixture composed of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280° C. and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

IV. 20 parts by weight of the active ingredient No. 5.13 are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene-α-sulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture which comprises 0.1% by weight of the active ingredient.

V. 3 parts by weight of the active ingredient No. 5.26 are mixed with 97 parts by weight of finely divided kaolin. This gives a dust which comprises 3% by weight of the active ingredient.

VI. 20 parts by weight of the active ingredient No. 5.24 are mixed intimately with 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenol/urea/formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. This gives a stable oily dispersion.

VII. 1 part by weight of the active ingredient No. 5.15 is dissolved in a mixture composed of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. This gives a stable emulsion concentrate.

VIII. 1 part by weight of the active ingredient No. 5.07 is dissolved in a mixture composed of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol® EM 31 (=nonionic emulsifier based on ethoxylated castor oil; BASF AG). This gives a stable emulsion concentrate.

The herbicidal compositions or the active ingredients of the formula I can be applied pre- or post-emergence. If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of spraying apparatus, in such a way that they come into as little contact as possible, if any, with the leaves of the sensitive crop plants, while the active ingredients reach the leaves of undesirable plants which grow underneath, or the exposed soil surface (post-directed, lay-by).

Depending on the intended purpose, the season, the target plants and the growth stage, the application rates of active ingredient of the formula I are from 0.001 to 3.0, preferably 0.01 to 1.0, kg of active substance (a.s.) per ha.

To widen the spectrum of action and to achieve synergistic effects, the hetaroyl derivatives of the formula I can be mixed with a large number of representatives of other groups of herbicidal or growth-regulating active ingredients and applied jointly. Suitable components for mixtures are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, (het)aryloxyalkanoic acids, and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2-(het)aroyl-1,3-cyclohexanediones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF₃-phenyl derivatives, carbamates, quinolinecarboxylic acid and its derivatives, chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- or hetaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonyl-ureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.

Furthermore, it may be advantageous to employ the compounds of the formula I, on their own or in combination with other herbicides, also in a mixture with other crop protection agents, for example pesticides or agents for controlling phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions which are employed for treating nutritional and trace element deficiencies. Nonphytotoxic oils and oil concentrates may also be added.

Use Examples

The herbicidal activity of the hetaroyl derivatives of the formula I was demonstrated by the following greenhouse experiments:

The culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.

In the case of pre-emergence treatment, the active ingredients, which were suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transluscent plastic hoods until the plants had rooted. This cover causes [sic] uniform germination of the test plants unless this was adversely affected by the active ingredients.

For the post-emergence treatment, the test plants were first grown to a plant height of from 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment. The application rate for the post-emergence treatment was 0.125 or 0.0625 kg of a.s. (active substance) per ha.

Depending on the species, the plants were kept at from 10 to 25° C. or 20 to 35° C. The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.

Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the aerial parts, and 0 means no damage or normal course of growth.

The plants used in the greenhouse experiments belong to the following species:

Scientific Name Common Name Chenopodium album lambsquarters (goosefoot) Echinochloa crus-galli barnyardgrass Polygonum persicaria ladysthumb Triticum aestivum summer wheat Zea mays Indian corn

At application rates of 0.125 or 0.0625 kg/ha, the compound 5.01 (Table 5) had a very good activity against the abovementioned mono- and dicotyledonous harmful plants and very good tolerability in summer wheat and maize when applied post-emergence. 

We claim:
 1. Hetaroyl derivatives of the formula

where: R¹ and R² are each hydrogen, nitro, halogen, cyano, thiocyanato, hydroxyl, mercapto, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₂-C₆-alkenyloxy, C₂-C₆-alkynyloxy, C₁-C₆-alkylthio, C₁-C₆-haloalkylthio, C₂-C₆-alkenylthio, C₂-C₆-alkynylthio, C₁-C₆-alkylsulfinyl, C₁-C₆-haloalkylsulfinyl, C₂-C₆-alkenylsulfinyl, C₂-C₆-alkynylsulfinyl, C₁-C₆-alkylsulfonyl, C₁-C₆-haloalkylsulfonyl, C₂-C₆-alkenylsulfonyl, C₂-C₆-alkynylsulfonyl, C₁-C₆-alkoxysulfonyl, C₁-C₆-haloalkoxysulfonyl, C₂-C₆-alkenyloxysulfonyl, C₂-C₆-alkynyloxysulfonyl, phenyl, phenyloxy, phenylthio, phenylsulfinyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following groups: nitro, cyano, hydroxyl, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy; Z is a building block from the group consisting of Z¹ to Z¹²

where R³, R⁵, R⁷ and R⁹ are each nitro, cyano, hydroxyl, mercapto, C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₂-C₄-alkenyloxy, C₂-C₄-alkynyloxy, C₂-C₄-alkenylthio, C₂-C₄-alkynylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-haloalkylsulfinyl, C₂-C₄-alkenylsulfinyl, C₂-C₄-alkynylsulfinyl, C₁-C₄-alkylsulfonyl, C₁-C₄-haloalkylsulfonyl, C₂-C₄-alkenylsulfonyl, C₂-C₄-alkynylsulfonyl, C₁-C₄-alkoxysulfonyl, C₁-C₄-haloalkoxysulfonyl, C₂-C₄-alkenyloxysulfonyl, C₂-C₄-alkynyloxysulfonyl, —NR¹²R¹³, —CO₂R¹², —CONR¹²R¹³, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following groups: nitro, cyano, hydroxyl, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy; or one of the radicals mentioned under R⁴; R⁴, R⁶, R⁸ and R¹⁰ are each hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio or C₁-C₄-haloalkylthio; or a —CR³R⁴—, —CR⁵R⁶—, —CR⁷R⁸— or —CR⁹R¹⁰— unit may be replaced by C═O or C═NR¹³; R¹¹ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₆-alkylcarbonyl, C₁-C₆-haloalkylcarbonyl, 13 CO₂R¹², —CONR¹²R¹³ or SO₂R¹²; R¹² is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl or phenyl, where the last radical may be partially or fully halogenated and may carry one to three of the following radicals: nitro, cyano, hydroxyl, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy; R¹³ is C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy or one of the radicals mentioned under R¹²; Q is a hydroxypyrazole, linked through position 4, of the formula II

where R¹⁴ is C₁-C₆-alkyl, C₁-C₆-haloalkyl or phenyl, where the last radical may be partially or fully halogenated and may carry one to three of the following radicals: nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy; R¹⁵ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkylcarbonyl, C₁-C₆-haloalkylcarbonyl, C₁-C₆-alkoxycarbonyl, C₁-C₆-alkylsulfonyl, C₁-C₆-haloalkylsulfonyl, phenyl-C₁-C₄-alkyl, phenylcarbonyl-C₁-C₄-alkyl, phenylcarbonyl, phenoxycarbonyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following radicals: nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy; R¹⁶ is hydrogen, C₁-C₆-alkyl or C₁-C₆-haloalkyl; and their agriculturally useful salts.
 2. Hetaroyl derivatives of the formula I as claimed in claim 1, where: R¹ and R² are each hydrogen, nitro, halogen, cyano, thiocyanato, hydroxyl, mercapto, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₂-C₆-alkenyloxy, C₂-C₆-alkynyloxy, C₁-C₆-alkylthio, C₁-C₆-haloalkyl-thio, C₂-C₆-alkenylthio, C₂-C₆-alkynylthio, C₁-C₆-alkylsulfinyl, C₁-C₆-haloalkylsulfinyl, C₂-C₆-alkenylsulfinyl, C₂-C₆-alkynylsulfinyl, C₁-C₆-alkylsulfonyl, C₁-C₆-haloalkylsulfonyl, C₂-C₆-alkenylsulfonyl, C₂-C₆-alkynylsulfonyl, C₁-C₆-alkoxysulfonyl, C₁-C₆-haloalkoxysulfonyl, C₂-C₆-alkenyloxysulfonyl, C₂-C₆-alkynyloxysulfonyl, phenyl, phenyloxy, phenylthio, phenylsulfinyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following groups: nitro, cyano, hydroxyl, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy; Z is a building block from the group consisting of Z¹ to Z¹²

where R³, R⁵, R⁷ and R⁹ are each hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, nitro, cyano, hydroxyl, mercapto, C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₂-C₄-alkenyloxy, C₂-C₄-alkynyloxy, C₂-C₄-alkenylthio, C₂-C₄-alkynylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-haloalkylsulfinyl, C₂-C₄-alkenylsulfinyl, C₂-C₄-alkynylsulfinyl, C₁-C₄-alkylsulfonyl, C₁-C₄-haloalkylsulfonyl, C₂-C₄-alkenylsulfonyl, C₂-C₄-alkynylsulfonyl, C₁-C₄-alkoxysulfonyl, C₁-C₄-haloalkoxysulfonyl, C₂-C₄-alkenyloxysulfonyl, C₂-C₄-alkynyloxy-sulfonyl, —NR¹²R¹³, —CO₂R¹², —CONR¹²R¹³, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following groups: nitro, cyano, hydroxyl, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy; R⁴, R⁶, R⁸ and R¹⁰ are each hydrogen; R¹¹ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₆-alkylcarbonyl, C₁-C₆-haloalkylcarbonyl, —CO₂R¹², —CONR¹²R¹³ or SO₂R¹²; R¹² is hydrogen, C₁-C₆-alkyl, C₁-C6-haloalkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl or phenyl, where the last radical may be partially or fully halogenated and may carry one to three of the following radicals: nitro, cyano, hydroxyl, C₁-C₄-alkyl, C₁-c₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy; R¹³ is C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy or one of the radicals mentioned under R¹²; R¹⁴ is C₁-C₆-alkyl, C₁-C₆-haloalkyl or phenyl, where the last substituent may be partially or fully halogenated and may carry one to three of the following radicals: nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C4-haloalkoxy; R¹⁵ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkylcarbonyl, C₁-C₆-haloalkylcarbonyl, C₁-C₆-alkoxycarbonyl, C₁-C₆-alkylsulfonyl, C₁-C₆-haloalkylsulfonyl, phenyl-C₁-C₄-alkyl, phenylcarbonyl-C₁-C₄-alkyl, phenylcarbonyl, phenoxycarbonyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following radicals: nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy; R¹⁶ is hydrogen, C₁-C₆-alkyl or C₁-C₆-haloalkyl.
 3. Hetaroyl derivatives of the formula I as claimed in claim 1, wherein the variable Z is Z¹, Z², Z¹¹ or Z¹².
 4. Hetaroyl derivatives of the formula I as claimed in claim 1, wherein the variable Z is Z³, Z⁴, Z⁵, Z⁶, Z⁷ or Z⁸.
 5. Hetaroyl derivatives of the formula I as claimed in claim 1, wherein the variable Z is z³, Z⁵, Z⁶, Z⁷ or Z⁸.
 6. Hetaroyl derivatives of the formula I as claimed in claim 1, wherein the variable Z is Z⁹ or Z¹⁰.
 7. Hetaroyl derivatives of the formula Ia as claimed in claim 1 and their N-oxides (formula Ia′)


8. Hetaroyl derivatives of the formula Ib as claimed in claim 1 and their N-oxides (formula Ib′)


9. Hetaroyl derivatives of the formula Ic as claimed in claim 1 and their N-oxides (formula Ic′)


10. Hetaroyl derivatives of the formula Id as claimed in claim 1 and their N-oxides (formula Id′)


11. Hetaroyl derivatives of the formula Ie as claimed in claim 1 and their N-oxides (formula Ie′)


12. Hetaroyl derivatives of the formula If (where Z=Z⁹) or Ig (where Z=Z¹⁰) as claimed in claim 1


13. A process for preparing hetaroyl derivatives of the formula I (where R¹⁵=H) as claimed in claim 1, which comprises acylating a hydroxypyrazole of the formula II (where R¹⁵=H)

with an activated carboxylic acid IIIa or with a carboxylic acid IIIb

where the variables R¹, R² and Z are each as defined in claim 1 and L¹ is a nucleophilically replaceable leaving group and the acylation product is rearranged in the presence of a catalyst to give the compounds I.
 14. A process for preparing hetaroyl derivatives of the formula I (where R¹⁵≠H) as claimed in claim 1, which comprises reacting a hetaroyl derivative of the formula I (where R¹⁵=H)

with a compound of the formula IV (where R¹⁵≠H) L²—R¹⁵ IV (where R¹⁵≠H) where L² is a nucleophilically replaceable leaving group.
 15. A herbicidal composition comprising a herbicidally active amount of at least one hetaroyl derivative of the formula I or of an agriculturally useful salt of I as claimed in claim 1 and at least one inert liquid and/or solid carrier and, if desired, at least one surfactant.
 16. A process for preparing herbicidally active compositions as claimed in claim 15, which comprises mixing a herbicidally active amount of at least one hetaroyl derivative of the formula I or of an agriculturally useful salt of I

and at least one inert liquid and/or solid carrier and, if desired, at least one surfactant.
 17. A method for controlling undesirable plant growth, which comprises allowing a herbicidally active amount of at least one hetaroyl derivative of the formula I or of an agriculturally useful salt of I as claimed in claim 1 act on plants, their habitat or on seeds. 